CN103035516A - Method and apparatus for etching silicon-containing film - Google Patents

Method and apparatus for etching silicon-containing film Download PDF

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Publication number
CN103035516A
CN103035516A CN2012105547519A CN201210554751A CN103035516A CN 103035516 A CN103035516 A CN 103035516A CN 2012105547519 A CN2012105547519 A CN 2012105547519A CN 201210554751 A CN201210554751 A CN 201210554751A CN 103035516 A CN103035516 A CN 103035516A
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gas
flow
velocity
fluorine
silicon
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功刀俊介
佐藤崇
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture 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
    • H01L21/18—Manufacture 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture 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
    • H01L21/18—Manufacture 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
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment 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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • H01L21/32137—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas of silicon-containing layers

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  • Physics & Mathematics (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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Abstract

Disclosed are a method and an apparatus for etching a silicon-containing film such as a silicon film or a silicon oxide film at a high rate without leaving residues, while suppressing etching of a base film. A silicon-containing film (93) on a base film (92) is etched by bringing a process gas, which contains a fluorine-based reaction component and an oxidizing reaction component, into contact with an object (90) to be processed. The flow rate of the process gas on the object (90) to be processed is changed by a flow rate-regulating means (60) in accordance with the progress of the etching. Preferably, the gas flow rate is changed by regulating the amount of the process gas flow. More preferably, the amount of the process gas flow is regulated by mixing a flow rate-regulating gas into a process gas supply system (10) or by stopping the mixing.

Description

The Etaching device of silicon-containing film
The application is dividing an application of 200980132762.4 (PCT/JP2009/054089), and the applying date of original application is on March 4th, 2009, and the denomination of invention of original application is engraving method and the device of silicon-containing film.
Technical field
The silicon-containing film that the present invention relates to unformed silicon or silica etc. are contained silicon atom carries out etching method and device.
Background technology
Silicon oxide film can be that the processing gas of reacting gas carries out etching by containing the fluorine such as hydrogen fluoride.Silicon fiml that unformed silicon etc. almost all are made of silicon atom can be that the processing gas of the oxidative reaction gases such as reacting gas and ozone carries out etching by having mixed the fluorine such as hydrogen fluoride.
For example, in patent documentation 1,2, put down in writing: utilize ozone to make the silica of wafer surface, form silica (formula 1), use on this basis hydrofluoric acid to carry out etching.Hydrofluoric acid is evaporated in the hydrofluoric acid steam generator, again it is imported wafer surface.
Put down in writing in the patent documentation 3: by at CF 4Be to cause near the discharge atmospheric pressure in the gas and generate HF, COF in fluorine 2Deng, COF 2Be mixed in advance CF 4Deng in water reaction and generate HF (formula 2), by the HF that is obtained by aforesaid way silica is carried out etching (formula 3).
Si+2O 3→ SiO 2+ 2O 2(formula 1)
COF 2+ H 2O → CO 2+ 2HF (formula 2)
SiO 2+ 4HF+H 2O → SiF 4+ 3H 2O (formula 3)
In patent documentation 4, put down in writing: by the CF of atmospheric plasma discharge after by humidification 4Obtain HF (formula 4), again to wherein adding O 3, silica is carried out etching.
CF 4+ 2H 2O → 4HF+CO 2(formula 4)
Put down in writing in the patent documentation 5: make CF 4And O 2Carry out atmosphere pressure discharging and obtain free radical, again it is imported the substrate that temperature is 20 ℃ or 100 ℃ from plasma space, monocrystalline silicon is carried out etching.
In patent documentation 6, put down in writing: make humidification CF 4Or dry CF 4Carry out atmosphere pressure discharging, under 90 ℃ of substrate temperatures, silicon metal is carried out etching.
Put down in writing in the patent documentation 7: in low-pressure chamber, silicon is carried out in the etched process, when basilar memebrane exposes or before basilar memebrane exposes, with the composition of etching gas be replaced as with respect to choice of the substrates than high gaseous species after, carried out etching.
The prior art document
Patent documentation 1: JP 2003-264160 communique
Patent documentation 2: JP 2004-55753 communique
Patent documentation 3: JP 2000-58508 communique
Patent documentation 4: JP 2002-270575 communique
Patent documentation 5: Unexamined Patent 04-358076 communique
Patent documentation 6: JP 2000-164559 communique
Patent documentation 7: JP 2002-343798 communique
Summary of the invention
The problem that invention will solve
In the etching of the silicon-containing film of unformed silicon or silica etc., being added on for generating fluorine is that the fluorine of reacted constituent is the water (with reference to formula 4) of raw material or passes through the surface that water (with reference to formula 3) that etching reaction generates can be attached to silicon-containing film and condense.The position of the water layer that condenses in existence, etching reaction is hindered.Therefore, the whole silicon-containing film of etching equably, the part of silicon-containing film is easily with mottled residual.
Although consider that also carrying out drying process when the surface attachment moisture at silicon-containing film removes moisture, the processing time is long, and is impracticable.
If carried out fully etching, then can remove with mottled residual silicon-containing film by etching, but basilar memebrane also can be by over etching.
Because the impact of substrate constituent of the film etc., in the washy situation, silicon-containing film increases than meeting with respect to the selection of basilar memebrane.
For the means of dealing with problems
In order to solve above-mentioned problem, the present invention is that a kind of object being treated to stacked silicon-containing film on the basilar memebrane carries out etching method, it is characterized in that, make that to contain fluorine be that the processing gas of reacted constituent contacts with described object being treated, the flow velocity of described processing gas on object being treated changed according to etched carrying out.
Owing to etching has produced water (with reference to formula 3).Sometimes in processing gas, also contain moisture (with reference to formula 4) in addition.At this, when the flow velocity of processing gas on object being treated increased, above-mentioned moisture easily dispersed from the surface of object being treated under the imposing manner of processing gas.Therefore, be attached to the amount of moisture on the surface of object being treated by flow velocity capable of regulating that regulate to process gas.In the stage that does not affect basilar memebrane, as long as can make the good mode of amount of moisture set the flow velocity of processing gas with the etch-rate of silicon-containing film.Thus, the processing time can be shortened.In the stage that affects basilar memebrane, make the larger mode of amount of moisture set the flow velocity of processing gas with silicon-containing film with respect to the etched selection specific energy of basilar memebrane and get final product.Thus, can suppress the etching of basilar memebrane, and can prevent that silicon-containing film is with mottled residual.
As the siliceous thing that consists of described silicon-containing film, can enumerate silicon (Si), silica (SiO 2), carborundum (SiC), silicon oxide carbide (SiOC), fire sand (SiCN) etc.Silicon (Si) can be unformed silicon, also can be polysilicon, also can be monocrystalline silicon.When described silicon-containing film was silicon (Si), carborundum (SiC), silicon oxide carbide (SiOC), fire sand (SiCN) etc., described processing gas preferably also contained the oxidative reaction composition.The oxidative reaction composition is for having the gas componant of oxidation to materials such as silicon.Thus, can make silicon-containing film oxidation (with reference to formula 1), then similarly carry out etching (with reference to formula 3) with silica.Carborundum (SiC) or silicon oxide carbide (SiOC) can be converted into silicon (Si) by heating, then similarly carry out etching (with reference to formula 1, formula 3) with silicon.As the oxidative reaction composition, can enumerate O 3, O free radical, H 2O 2, O 2, NO 2, N 2O etc. preferably enumerate O 3
Basilar memebrane if by from consist of as the different composition of the silicon-containing film of etch target, also can be siliceous thing.When being silicon (Si) as the silicon-containing film of etch target, basilar memebrane for example is silica (SiO 2), silicon nitride (SiN) etc.Silicon-containing film as etch target is silica (SiO 2) time, basilar memebrane is for such as silicon nitride (SiN) etc.When being carborundum (SiC) or silicon oxide carbide (SiOC) as the silicon-containing film of etch target, basilar memebrane is for example silicon nitride (SiN), silica (SiO 2) etc.
Described flow velocity is carried out along with etched, and change interimly.Thus, coutroi velocity easily." stage " refers to that being changed to of described flow velocity is discontinuous or stair-stepping.
Described flow velocity is carried out along with etched, change continuously.
The variation of flow velocity gets final product at least one times.The moment that changes is preferably determined by experiment in advance.
Preferably carry out along with etched, increase described flow velocity.
Thus, in the stage that does not affect basilar memebrane, can relatively reduce to process the flow velocity of gas, thereby can fully increase the amount of moisture on the surface that is attached to object being treated.Therefore, can improve the etch-rate of silicon-containing film.When arriving the stage that affects basilar memebrane along with etched carrying out, by relatively increasing the flow velocity of processing gas, moisture is dispersed from the surface of object being treated, thereby can reduce the attachment of moisture amount on object being treated surface.When basilar memebrane is made of silicon nitride etc., be accompanied by the minimizing of the attachment of moisture amount on object being treated surface, the reduction degree of the etch-rate of basilar memebrane is larger than the silicon-containing film that is made of silicon etc.Therefore, can increase silicon-containing film with respect to the etched selection ratio of basilar memebrane.Thus, the etching of crossing of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
Preferably carry out along with etched, increase described flow velocity interimly.Thus, coutroi velocity easily.
Also can carry out along with etched, increase gradually continuously described flow velocity.
Because the impact of substrate constituent of the film etc. is carried out along with etched, silicon-containing film is larger than change with respect to the selection of basilar memebrane, therefore, also can or reduce continuously described flow velocity interimly.
Preferably make to described silicon-containing film want major part (or roughly whole) in the etched part carry out etched during in the described flow velocity less of (hereinafter referred to as " the 1st etching work procedure "), make to described silicon-containing film want in the etched part behind described the 1st etching work procedure residual part carry out etched during in the described flow velocity of (hereinafter referred to as " the 2nd etching work procedure ") relatively large.
Thus, to silicon-containing film want major part in the etched part to carry out etching the time, can easily be attached to moisture the state on the surface of object being treated, positively improve etch-rate.Therefore, can positively shorten the processing time.Then, when residual silicon-containing film is carried out etching, moisture is dispersed from the surface of object being treated, can reduce the attachment of moisture amount on object being treated surface.Therefore, when basilar memebrane is made of silicon nitride etc., silicon-containing film with respect to the selection of basilar memebrane than increasing.Thus, the etching of crossing of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
At this, " major part " refers to for example 50～99.9% in the etched part of wanting of silicon-containing film, is preferably 70～99.9%, more preferably 80～99.9%, more preferably 90～99.9%." roughly whole " are the upper limit segment of above-mentioned " major part ", refer to for example 90～99.9% in the etched part of wanting of silicon-containing film.
In described the 1st etching work procedure, increase described flow velocity interimly, and make described flow velocity in described the 2nd etching work procedure greater than the flow velocity of the final stage of described the 1st etching work procedure.
Thus, the etching of crossing of basilar memebrane can be further positively suppressed, and the mottled residue of silicon-containing film can be positively prevented.
Preferably by making the changes in flow rate of described processing gas, make described change in flow.
Thus, can be simply and positively make change in flow.
Preferably be accompanied by etched carrying out, increase the flow of described processing gas.Preferably make the flow less of the processing gas in the 1st etching work procedure, make the flow of the processing gas in the 2nd etching work procedure relatively large.
Preferably mixture velocity is regulated with gas or is stopped to mix in described processing gas, and the flow of processing gas is changed.
Thus, how to change no matter process the flow of gas, the flow of processing the reacted constituent in the gas can not change substantially, therefore can suppress the change of the etch-rate of silicon-containing film.
Preferably carry out along with etched, increase the flow that described velocity of flow adjust is used gas.Preferably make the flow less of the velocity of flow adjust usefulness gas in the 1st etching work procedure, make the velocity of flow adjust in the 2nd etching work procedure relatively large with the flow of gas.
By described mixing, described velocity of flow adjust becomes a kind of composition in the described processing gas with gas.
Described fluorine is that reacted constituent can to contain fluorine be raw material and added H by making 2The fluorine of O is that near the plasma space that unstrpped gas is passed through the atmospheric pressure generates.
At the upstream side of described plasma space, be that mixture velocity is regulated with gas or stopped to mix in the unstrpped gas at described fluorine, according to the Flow-rate adjustment described flow velocity of this velocity of flow adjust with gas.
Because fluorine is the flow of raw material to be kept constantly, therefore can suppress the variation that fluorine is the growing amount of reacted constituent, thereby can suppress the change of the etch-rate of silicon-containing film.At this moment, it is the diluent gas of raw material that velocity of flow adjust can be for fluorine with gas, also can be the gas different from diluent gas.
Preferably in the downstream of described plasma space, mixture velocity is regulated with gas or is stopped to mix in described processing gas, according to the Flow-rate adjustment described flow velocity of this velocity of flow adjust with gas.
At this moment, no matter how described flow velocity changes, all can make flow-rate ratio and the flow of each composition that imports the gas in the plasma space keep constant.Thus, can make discharge stability in the plasma space.Thus, can further positively suppress the change of the etch-rate of silicon-containing film.
What be explained is that the velocity of flow adjust in the 1st etching work procedure can be zero with the flow of gas.
The present invention is that a kind of object being treated to stacked silicon-containing film on the basilar memebrane carries out etched device, it is characterized in that having: the processing gas that will contain fluorine and be reacted constituent is supplied in the processing gas delivery system of described object being treated; With make the flow velocity of described processing gas on object being treated according to the etched flow adjustment mechanism that changes of carrying out.
According to above-mentioned feature, by regulating described flow velocity, can regulate the attachment of moisture amount on object being treated surface.Thus, in the stage that does not affect basilar memebrane, can regulate so that the etch-rate of silicon-containing film is good.Processing time can be shortened thus.In the stage that affects basilar memebrane, can regulate so that silicon-containing film is good with respect to the selection ratio of basilar memebrane.Therefore, the etching of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
Described flow adjustment mechanism preferably makes described flow velocity along with etched carrying out changes interimly.Thus, coutroi velocity governor motion easily.
Described flow adjustment mechanism also can make described flow velocity change continuously along with etched.
Described flow adjustment mechanism preferably makes described flow velocity increase along with etched.
Thus, in the stage that does not affect basilar memebrane, make the flow velocity less of processing gas, increase the amount of moisture on the surface that is attached to object being treated, thereby improve the etch-rate of silicon-containing film.Therefore, can positively shorten the processing time.Carry out along with etched, arrive when affecting the stage of basilar memebrane, process the flow velocity of gas by relatively increase, thereby moisture is dispersed from the surface of object being treated, can reduce the attachment of moisture amount on object being treated surface.Therefore, when basilar memebrane is made of silicon nitride etc., can improve silicon-containing film with respect to the selection ratio of basilar memebrane.Thus, the etching of crossing of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
Described flow adjustment mechanism is preferably carried out along with etched, increases described flow velocity interimly.Thus, coutroi velocity governor motion easily.
Described flow adjustment mechanism is preferably carried out along with etched, little by little increases continuously described flow velocity.
Because the impact of substrate constituent of the film etc. is carried out along with etched, silicon-containing film is larger than change with respect to the selection of basilar memebrane, thereby described flow adjustment mechanism also can or reduce described flow velocity continuously interimly.
Most of etched in the etched part wanted of the preferred until described silicon-containing film of described flow adjustment mechanism makes described flow velocity less, makes described flow velocity relatively large when the silicon-containing film of etch residue.
Thus, to silicon-containing film want major part in the etched part to carry out etching the time, can increase the attachment of moisture amount on object being treated surface, positively improve etch-rate.Therefore, can positively shorten the processing time.Then, during the silicon-containing film of etch residue, moisture is dispersed from the surface of object being treated, thereby can reduce the attachment of moisture amount on object being treated surface.Therefore, when basilar memebrane is made of silicon nitride etc., can increase silicon-containing film with respect to the selection ratio of basilar memebrane.Thus, the etching of crossing of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
Described flow adjustment mechanism is preferably the flow control device of the flow of regulating described processing gas.
Thus, flow adjustment mechanism can adopt easy structure, and can positively change flow velocity.
Described flow adjustment mechanism (flow control device) is preferably carried out along with etched, increases the flow of described processing gas.
Described flow adjustment mechanism (flow control device), preferred until at the most of etched flow less that makes described processing gas in the etched part wanted of described silicon-containing film, when the silicon-containing film of etch residue, make the flow of described processing gas relatively large.Described flow adjustment mechanism also can be carried out along with etched, reduces the flow of described processing gas.
Described processing gas delivery system preferably comprises: the plasma generating unit that forms near the plasma space of atmospheric pressure; With with become described fluorine be reacted constituent to contain fluorine be raw material and added H 2The fluorine of O is the feed line that unstrpped gas imports described plasma space.
Described flow adjustment mechanism mixture velocity in described feed line is regulated with gas or is stopped to mix, and regulates described flow velocity according to this velocity of flow adjust with the flow of gas.
Thus, can make fluorine be that the flow of raw material is kept constant, can suppress fluorine is the change of the growing amount of reacted constituent, suppresses the change of the etch-rate of silicon-containing film.
Described velocity of flow adjust consists of a kind of composition of described processing gas with gas.
Described velocity of flow adjust quality award from the ministry is selected in the processing gas delivery system in downstream of described plasma space mixture velocity and regulates with gas or stop to mix, according to the Flow-rate adjustment described flow velocity of this velocity of flow adjust with gas.
Thus, no matter how described flow velocity changes, all can make flow-rate ratio and the flow of each composition of the gas that imports plasma space keep constant.Therefore, can make discharge stability in the plasma space.Thus, can further positively suppress the change of the etch-rate of silicon-containing film.
Apparatus of the present invention are that the object being treated to stacked silicon-containing film on basilar memebrane carries out etched device, it is characterized in that, comprising: a plurality of processing gas delivery systems, its ejection contain the processing gas that fluorine is reacted constituent; Switching mechanism, it will be processed gas and blow the processing gas delivery system that is attached to described object being treated according to etched optionally the switching, wherein, blown when being attached to object being treated from least 2 in the described a plurality of processing gas delivery systems processing gases of processing the gas delivery systems, the flow velocity on object being treated is different.
According to this feature, by selecting described processing gas delivery system, can regulate to blow the flow velocity of processing gas on object being treated that invests object being treated.According to the difference of this flow velocity, can regulate the attachment of moisture amount on object being treated surface.Thus, in the stage that does not affect basilar memebrane, can regulate so that the etch-rate of silicon-containing film is good.Therefore, the processing time can be shortened.In the stage that affects basilar memebrane, can regulate so that silicon-containing film is good with respect to the selection ratio of basilar memebrane.Therefore, the etching of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
Described switching mechanism is preferably selected along with the etched relatively large processing gas delivery system of described flow velocity that carries out.
Thus, in the stage that does not affect basilar memebrane, the processing gas by the little delivery system of self-flow rate in future blows and is attached to object being treated, thereby can improve the attachment of moisture amount on object being treated surface, can positively improve the etch-rate of silicon-containing film.Therefore, can positively shorten the processing time.Carry out along with etched, arrive when affecting the stage of basilar memebrane, the processing gas by the large delivery system of self-flow rate in future blows and is attached to object being treated, and moisture is dispersed from the surface of object being treated, can reduce the attachment of moisture amount on object being treated surface.Therefore, when basilar memebrane is made of silicon nitride etc., can increase silicon-containing film with respect to the selection ratio of basilar memebrane.Thus, the etching of crossing of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
Preferred described switching mechanism is until at the most of etched processing gas delivery system of selecting described flow velocity less in the etched part wanted of described silicon-containing film, select the relatively large processing gas delivery system of described flow velocity when the silicon-containing film of etch residue.Thus, etching silicon-containing film want most of in the etched part time, can increase the attachment of moisture amount on object being treated surface, thereby positively improve etch-rate.Therefore, can positively shorten the processing time.During the silicon-containing film of etch residue, moisture from the surface of object being treated dispersed, can reduce the attachment of moisture amount on object being treated surface thereafter.Therefore, when basilar memebrane is made of silicon nitride etc., can increase silicon-containing film with respect to the selection ratio of basilar memebrane.Thus, the etching of crossing of basilar memebrane can be suppressed, and the mottled residue of silicon-containing film can be positively prevented.
The flow of the processing gas of at least 2 processing gas delivery systems in preferred described a plurality of processing gas delivery systems is different.
Thus, by hand-off process gas delivery system the flow of the processing gas that is sprayed onto object being treated is changed, process the change in flow of gas on object being treated thereby can make.Described switching mechanism is preferably selected the relatively large processing gas delivery system of flow of processing gas along with etched.Described switching mechanism also can be selected the processing gas delivery system of processing the flow less of gas along with etched.
The body delivery system of regulating the flow of vital energy everywhere also can comprise the plasma generating unit that forms near the plasma space of atmospheric pressure; With become described fluorine be reacted constituent to contain fluorine be raw material and added H 2The fluorine of O is the feed line that unstrpped gas imports described plasma space, and wherein, at least one feed line of processing the gas delivery system is connected with gas supply part with the velocity of flow adjust that makes velocity of flow adjust with the gas interflow.
Use the processing gas delivery system of gas supply part about having connected above-mentioned velocity of flow adjust, with be not connected velocity of flow adjust and compare with the processing gas delivery system of gas supply part, more easily increase the ejection flow of processing gas, and then more easily be increased in the gas flow rate on the object being treated.
The preferred body delivery system of regulating the flow of vital energy everywhere comprises the plasma generating unit that forms near the plasma space of atmospheric pressure; With with become described fluorine be reacted constituent to contain fluorine be raw material and added H 2The fluorine of O is the feed line that unstrpped gas imports described plasma space, wherein, the processing gas delivery system in the downstream of the described plasma space of at least one processing gas delivery system is connected with gas supply part with the velocity of flow adjust that makes velocity of flow adjust with the gas interflow.
For having connected above-mentioned velocity of flow adjust for the processing gas delivery system of gas supply part, with be not connected velocity of flow adjust and compare with the processing gas delivery system of gas supply part, more easily increase the ejection flow of processing gas, and then more easily increase the gas flow rate on object being treated.And, having connected above-mentioned velocity of flow adjust with in the processing gas delivery system of gas supply part, in the situation that plasma space does not import velocity of flow adjust gas, can make discharge stability, thus reaction of formation composition stably.
Having connected above-mentioned velocity of flow adjust can be more than 2 with the processing gas delivery system of gas supply part.At this moment, about at least 2 in this processing gas delivery system more than 2 processing gas delivery systems, can be different with the interflow amount of gas with the velocity of flow adjust of gas supply part from above-mentioned velocity of flow adjust.
Be raw material as described fluorine, can enumerate perfluorocarbon (PFC), HFC (HFC), SF 6, NF 3, XeF 2Deng.As PFC, can enumerate CF 4, C 2F 6, C 3F 6, C 3F 8Deng.As HFC, can enumerate CHF 3, C 2H 2F 2, CH 3F etc.
Also can replace H 2O and use the compound that contains OH.As the compound that contains the OH base, can enumerate aquae hydrogenii dioxidi, alcohol etc.
Be the diluent gas of raw material as described fluorine, except can enumerating the rare gas such as Ar, He, also can enumerate N 2Deng.
Be reacted constituent as fluorine, can enumerate HF, COF 2Deng.Diluent gas can be changed the flow of diluent gas with gas as described velocity of flow adjust.
When described siliceous thing was silicon, carborundum, silicon oxide carbide, fire sand etc., it was that the processing gas of reacted constituent and oxidative reaction composition is supplied in described object being treated that described processing gas delivery system preferably will contain fluorine.Thus, available oxidative reaction composition makes described siliceous thing oxidation (formula 1), then, is that reacted constituent carries out etching (formula 3) with fluorine again.
When described siliceous thing is carborundum, silicon oxide carbide etc., preferably also has heating arrangements.By heating object being treated with heating arrangements, can make the silication such as carborundum, silicon oxide carbide, then, can be that the situation of silicon is similarly carried out etching with siliceous thing.
When described siliceous thing was silicon, carborundum, silicon oxide carbide etc., preferred described feed line was unstrpped gas with described fluorine and becomes oxidative reaction composition (O 3, O free radical etc.) oxygen be that at least fluorine in the unstrpped gas is that unstrpped gas imports described plasma space.
Described velocity of flow adjust is with the preferred inert gas of gas or oxidative reaction gas.
As inert gas, except can enumerating the rare gas such as Ar, He, also can enumerate nitrogen (N 2).From reducing the viewpoint of running time, as becoming the inert gas of described velocity of flow adjust with gas, preferably use nitrogen.
Oxidative reaction gas contains described oxidative reaction composition (ozone (O 3), hydrogen peroxide (H 2O 2), oxygen (O 2) etc.), preferably contain ozone (O 3).Oxidative reaction gas also can contain multiple oxidative reaction composition, also can contain the material composition of oxidative reaction composition.For example, oxidative reaction gas can be ozone (O 3) and oxygen (O 2) mist.And then oxidative reaction gas can contain the inert gases such as nitrogen, Ar.
As mentioned above, through peroxidization and in the etched silicon-containing film of silicon (Si), carborundum (SiC), silicon oxide carbide (SiOC), fire sand (SiCN) etc. processed gas and contained and be useful on the oxidative reaction gas that causes described oxidation reaction.At this moment, by changing the flow of oxidative reaction gas, the flow of described processing gas is changed, and then described flow velocity is changed.Thus, oxidative reaction gas can be used with gas on behalf of velocity of flow adjust.Therefore, there is no need to prepare in addition the gas of velocity of flow adjust special use, the gaseous species that can reduce to use.In addition, how to change no matter process the flow of gas integral body, all can make fluorine is that unstrpped gas or fluorine are that the flow of reacting gas keeps constant.Therefore, can suppress the change of the etch-rate of silicon-containing film.
When in the etching that silicon-containing film is carried out, not needing the oxidative reaction composition, as velocity of flow adjust gas, also can use oxidative reaction gas.
Described processing gas delivery system comprises: the fluorine that will contain described fluorine and be reacted constituent is that the fluorine that reacting gas is supplied in described object being treated is the reacting gas delivery system; Be supplied in the oxidative reaction gas delivery system of described object being treated with the oxidative reaction gas that will contain the oxidative reaction composition, wherein, described flow adjustment mechanism can be regulated the supply gas flow of described oxidative reaction gas delivery system.
Thus, can carry out according to etched, change the supply flow rate of oxidative reaction gas, and then change the supply flow rate of processing gas integral body.Consequently, can regulate the flow velocity of processing gas.Oxidative reaction gas can be used for the etching (oxidation reaction) of silicon-containing film, use with gas as velocity of flow adjust.Therefore, do not need the gas of velocity of flow adjust special use, can reduce needed gaseous species.
Being reacting gas delivery system and oxidative reaction gas delivery system by the fluorine that minute is arranged, no matter how the flow of oxidative reaction gas to regulate, all can be that fluorine that the reacting gas delivery system is supplied with is that the flow of reacting gas keeps constant with fluorine.Thus, can suppress the change of the etch-rate of silicon-containing film.
Oxidative reaction gas can be by being that unstrpped gas is raw material take oxygen, and generate by gas excitation apparatus such as plasma generating unit or ozone generators.By import for example oxygen (O in the plasma generating unit 2) be that unstrpped gas is carried out plasma as oxygen, can generate the oxidative reaction gas that contains the oxidative reaction compositions such as oxygen radical.By in ozone generator, importing oxygen (O 2) be unstrpped gas as oxygen, can generate the oxidative reaction gas that is consisted of by gas ozoniferous.
Oxidative reaction gas on behalf of as velocity of flow adjust when using gas, also can be regulated oxygen and is the supply flow rate of unstrpped gas in plasma discharge section or the ozone generator.Thus, can regulate the flow of oxidative reaction gas, and then regulate the flow of processing gas.
Oxygen is that unstrpped gas is the gas that becomes the raw material of oxidative reaction gas.Be unstrpped gas as oxygen, can enumerate O 2, NO, NO 2, N 2O etc. are preferably O 2These oxygen are that unstrpped gas itself more or less all has oxidation, have the function as oxidative reaction gas.
Described feed line can be that unstrpped gas and described oxygen are the unstrpped gas mixing and import in the described plasma space with described fluorine.
Also can be that unstrpped gas is carried out plasma, excited activation or ozonisation with oxygen in the line different from described feed line, obtain described oxidative reaction composition.At this moment, can be reacted constituent with the fluorine from described feed line mixes with oxidative reaction composition from described other line, and then is supplied in object being treated, also can be supplied in object being treated from other blow-off outlet.
With oxidative reaction gas on behalf of as velocity of flow adjust when use gas, preferably at described other line generation oxidative reaction gas.Like this, no matter how the flow of oxidative reaction gas changes, all can positively make fluorine is that the formation efficiency of reacting gas is kept constant.And then, make the etch-rate of silicon-containing film stable.
Described processing gas delivery system (or described oxidative reaction gas delivery system) also can comprise the containers such as oxygen cylinder of accumulating oxidative reaction gas.Also can directly supply with oxidative reaction gas to object being treated from this container.Thus, can omit for the plasma discharge section or the ozone generator that generate oxidative reaction gas.
With oxidative reaction gas on behalf of when using gas, also regulating the supply flow rate from the oxidative reaction gas of described container as velocity of flow adjust.Supplying with the road from the oxidative reaction gas of described container is that the fluorine in the downstream of the reacting gas plasma generating unit that generates usefulness is that reacting gas is supplied with the interflow, road with fluorine preferably.
Refer to 1.013 * 10 near the atmospheric pressure 4～50.663 * 10 4The scope of Pa if consider the easiness of pressure adjustment, the simplicity of apparatus structure, is preferably 1.333 * 10 4～10.664 * 10 4Pa, more preferably 9.331 * 10 4～10.397 * 10 4Pa.
The invention effect
According to the present invention, can not have residue ground and with two-forty ground silicon-containing film is carried out etching, and can suppress the etching of basilar memebrane.
Description of drawings
[Fig. 1] Fig. 1 is the key diagram of the summary formation of expression the 1st execution mode of the present invention.
[Fig. 2] Fig. 2 (a) is the profile of the object being treated before the etching, the vertical view of the object being treated when Fig. 2 (b) is the end of the 1st etching work procedure, Fig. 2 (c) is the profile of Fig. 2 (b), the vertical view of the object being treated when Fig. 2 (d) is the end of the 2nd etching work procedure.
[Fig. 3] Fig. 3 is the key diagram of the summary formation of expression the 2nd execution mode of the present invention.
[Fig. 4] Fig. 4 is the key diagram of the summary formation of expression the 3rd execution mode of the present invention.
[Fig. 5] Fig. 5 is the key diagram of the summary formation of expression the 4th execution mode of the present invention.
[Fig. 6] Fig. 6 is the key diagram of the summary formation of expression the 5th execution mode of the present invention.
[Fig. 7] Fig. 7 is the key diagram of the summary formation of expression the 6th execution mode of the present invention.
[Fig. 8] Fig. 8 is the key diagram of the summary formation of expression the 7th execution mode of the present invention.
[Fig. 9] Fig. 9 is the key diagram of the summary formation of expression the 8th execution mode of the present invention.
[Figure 10] Figure 10 is the result's of expression embodiment 2 curve chart.
[Figure 11] Figure 11 is the result's of expression embodiment 3 curve chart.
Embodiment
Below, embodiments of the present invention are described.
The 1st execution mode
The present invention can be applicable in the etching of the silicon-containing film that object being treated forms.
One example of the object being treated 90 before Fig. 2 (a) expression etching.In the object being treated 90, the glass of for example using with flat-panel monitor forms basilar memebranes 92, stacked silicon-containing film 93 as etch target on this basilar memebrane 92 as substrate 91 at this glass substrate 91.Basilar memebrane 92 for example is made of silicon nitride (SiNx).Silicon-containing film 93 as etch target for example is made of unformed silicon (a-Si).Although omit in the diagram, in the silicon-containing film 93 of object being treated 90, should etched part do not covered by masks such as resists.Not concealed part becomes and wants etched part in the silicon-containing film 93.
Fig. 1 is illustrated in an example of the Etaching device 1 that uses in the etching of silicon-containing film 93.Etaching device 1 has the gas delivery system 10 of processing and support portion 20.Object being treated 90 is being supported in support portion 20.Support portion 20 for example is made of objective table.The inside of support portion 20 is provided with heating part 21.Can heat object being treated 90 by heating part 21.
Process gas delivery system 10 and comprise feed line 30 and plasma generating unit 40.It is raw material supplying section 31 that the upstream extremity of feed line 30 is provided with fluorine.Fluorine is that raw material supplying section 31 is that unstrpped gas is delivered to feed line 30 with fluorine.Be raw material as fluorine, can enumerate CF 4, CHF 3, C 2F 6, C 3F 8, SF 6, NF 3, XeF 2Deng.At this, be raw material as fluorine, use CF 4Fluorine is that raw material can be used Ar, He, N 2Dilute Deng diluent gas, also can not dilute.At this, be unstrpped gas as fluorine, can use the CF that has been diluted by Ar 4CF 4Be preferably CF with the volumetric mixture ratio of Ar 4: Ar=5: 95～80: 20, CF more preferably 4: Ar=10: 90～30: 70.
Feed line 30 is connected with addition portion 32.Addition portion 32 is by having accumulated liquid water (H 2O) humidifier consists of, and it makes the liquid water vaporization, and the fluorine that makes an addition to feed line 30 is unstrpped gas (CF 4+ Ar) in.As the method for adding, can make the fluorine that flows through feed line 30 is that the part of unstrpped gas is shunted in addition portion 32, this shunting gas is contacted with the liquid level of addition portion 32, water is vaporized in shunting gas, also shunting gas can be carried out bubbling and makes water vapor in the water of addition portion 32.Also available heater heating water and make its vaporization and be supplied in feed line 30.
Connecting aerobic in the downstream of the addition portion 32 of feed line 30 is raw material supplying section 34.Raw material supplying section 34 is that unstrpped gas is supplied in feed line 30 with oxygen.Thus, can be that unstrpped gas and oxygen are unstrpped gas at feed line 30 interior mixing fluorine.Be raw material as oxygen, can enumerate O 2, NO, NO 2, N 2O etc.At this, be unstrpped gas as oxygen, can use O 2Gas.Oxygen is the upstream side that raw material supplying section 34 and the connecting portion of feed line 30 can be positioned at addition portion 32.
Feed line 30 is connected with gas supply part 60 (flow adjustment mechanism) with velocity of flow adjust.Velocity of flow adjust is positioned at the downstream of water addition portion 32 with gas supply part 60 and the connecting portion of feed line 30, and be positioned at oxygen is the downstream of the connecting portion of raw material supplying section 34, but be not limited thereto, can be the upstream side of raw material supplying section 34 at oxygen also, also can be at the upstream side of water addition portion 32.
Velocity of flow adjust is accumulated velocity of flow adjust gas with gas supply part 60.Velocity of flow adjust is preferably inert gas with gas.As inert gas, except can enumerating the rare gas such as Ar, He, also can enumerate N 2At this, as velocity of flow adjust gas, use N 2
Velocity of flow adjust can have in feed line 30 mixture velocity with gas supply part 60 to be regulated with the mixed mode of gas and this two states of stop mode that stops to mix.Although omitted detailed diagram, can switch valve or flow control valve be set in gas supply part 60 at velocity of flow adjust.By these valves, can select any pattern in mixed mode and the stop mode, or regulate the velocity of flow adjust gas (N in the mixed mode 2) flow.Fluorine is unstrpped gas (CF 4+ Ar) with velocity of flow adjust with gas (N 2) mixing ratio preferably set at (CF 4+ Ar): N 2=10: 1～2: in 1 the scope.
The downstream of feed line 30 is extended to plasma generating unit 40.
Plasma generating unit 40 has mutual opposed pair of electrodes 41,41.Opposed faces at least one party's electrode 41 is provided with solid dielectric layer (not shown).Side in these electrodes 41,41 is connected with power supply 42, and the opposing party electrical ground.By utilizing power supply 42 service voltages, the space 43 between the electrode 41,41 becomes near the plasma space the atmospheric pressure.Upstream extremity at plasma space 43 links to each other with feed line 30.The downstream of plasma space 43 is provided with the blowing unit 59 that is made of nozzle.The object being treated 90 of blowing unit 59 on the support portion 20.The mode that blowing unit 59 can move back and forth between the two ends of support portion 20 is with respect to support portion 20 relatively move (scanning).
Although omitted diagram, the area of certain degree is held in the bottom surface of blowing unit 59, and forms the gas road between the object being treated 90., in the above-mentioned gas road, flow to the direction away from the opening of blowing unit 59 along the surface of object being treated 90 from the processing gas of the opening of blowing unit 59 ejection.
Use the Etaching device 1 of above-mentioned formation, illustrate that the silicon-containing film 93 to object being treated 90 carries out etching method.
Etched operation is divided into the 1st etching work procedure in from the etched initial stage to mid-term (before latter stage) and the 2nd etching work procedure that carries out latter stage in etching.
[the 1st etching work procedure]
In the 1st etching work procedure, be unstrpped gas (CF with fluorine 4+ Ar) be that raw material supplying section 31 is delivered to feed line 30 from fluorine.Utilizing addition portion 32 is to add water (H in the unstrpped gas at this fluorine 2O).The addition of water is regulated by addition portion 32.The addition of water is many as far as possible in the scope that does not produce dewfall.Preferably making fluorine is that to contain dew point temperature be 10～50 ℃ moisture to unstrpped gas.Fluorine is that preferably the temperature than atmosphere temperature or object being treated 90 is low for the dew point temperature of unstrpped gas.Thus, can prevent in consisting of the pipe arrangement of feed line 30 or the surface of object being treated 90 produces dewfall.In the situation that object being treated 90 is not heated section's 21 heating, during room temperature, the dew point that preferred fluorine is unstrpped gas is 15～20 ℃.
Fluorine after adding water is unstrpped gas (CF 4+ Ar+H 2O) mixing in from oxygen is that the oxygen of raw material supplying section 34 is unstrpped gas (O 2), generate mixed material gas.Fluorine is that unstrpped gas and oxygen are that to be preferably fluorine be unstrpped gas for the volumetric mixture ratio of unstrpped gas: oxygen is unstrpped gas=1: 9～9: 1, and more preferably fluorine is unstrpped gas: oxygen is unstrpped gas=1: 2～2: 1.The volume ratio of water is that unstrpped gas and oxygen are that unstrpped gas is enough little with respect to fluorine, and the fluorine that therefore adds before the water is that unstrpped gas and oxygen are the volume ratio of unstrpped gas, is that unstrpped gas and oxygen are that the volume ratio of unstrpped gas is roughly the same with adding fluorine behind the water.
In the 1st etching work procedure, velocity of flow adjust adopts stop mode with gas supply part 60, stops first velocity of flow adjust gas (N 2) mixing in the feed line 30.Above-mentioned mixed material gas (CF 4+ Ar+O 2+ H 2O) velocity of flow adjust is arranged with gas (N unmixed 2) situation under directly be imported into inter-electrode space 43 from the downstream of feed line 30.
Meanwhile, by power supply 42 to electrode 41 service voltages, near plasma inter-electrode space 43 interior generation atmospheric pressure.Thus, mist is by plasma (comprise decomposition, excite, activation, free radical, ionization etc.), generates to comprise the processing gas that fluorine is reacted constituent and oxidative reaction composition.Below, the processing gas of the 1st etching work procedure suitably is called " the 1st processes gas ".The 1st processes gas formation can be with the prescription of two-forty etching silicon 93.Be reacted constituent as fluorine, can enumerate HF, COF 2Deng.These fluorine are that reacted constituent mainly is by CF 4And H 2O decomposes and generates.As the oxidative reaction composition, can enumerate O 3, O free radical etc.These oxidative reaction compositions mainly are with O 2For raw material generates.
The 1st processes gas from 40 ejections of plasma generating unit, and is sprayed onto the object being treated 90 on the support portion 20.The 1st processes gas flows on the surface of object being treated 90.Object being treated 90 gas flow rate from the teeth outwards is less than the 2nd etching work procedure described later.The 1st oxidative reaction composition of processing in the gas contacts with the silicon-containing film 93 that is made of unformed silicon, causes the oxidation reaction of silicon, thereby generates silica (formula 1).This silica is that reacted constituent contacts (formula 3) with fluorine, generates volatile SiF 4Like this, silicon-containing film 93 is just etched with good etch-rate.
The 1st processes the composition that can contain the mixed material gas that does not have decomposition in plasma space 43 in the gas, therefore also can contain water.The part of described water and fluorine are the COF of reacted constituent 2Reaction generates HF (formula 2), helps the etching of silicon.The part of remaining water is attached to the surface of object being treated 90 and condenses.In addition, generate water by the etching reaction (formula 3) based on HF, the part of these water also is attached to the surface of object being treated 90 and condenses.Thus, can form on the surface of object being treated 90 condensed layer of water.The 1st to process gas be the size of the moisture degree of substantially not dispersing on the surface of object being treated 90 at the flow velocity on the object being treated 90.Therefore, can make condensed layer possess suitable thickness, improve fully the etch-rate of silicon.
On the other hand, in some place on the surface of object being treated 90, the condensed layer of water forms blocked uply sometimes.And be obstructed at the position of the bed thickness that condenses etching reaction.Therefore, such as Fig. 2 (b) and with shown in the figure (c), there is the position that basilar memebrane 92 exposes in the surface of the object being treated 90 before etching reaches latter stage and wants still residual position of etched silicon-containing film 93.Residual silicon-containing film 93 is called residual film 93a.Residual film 93a is mottled (graniphyric).
[the 2nd etching work procedure]
Such as Fig. 2 (b) and with shown in the figure (c), carry out along with etched, when the part of basilar memebrane 92 is exposed or before exposing, switch to the 2nd etching work procedure from the 1st etching work procedure.Can detect basilar memebrane 92 expose or on basilar memebrane 92 residual silicon-containing film 93 thickness and switch to the 2nd etching work procedure, also can wait by experiment in advance moment of come to determine switching, constantly switch to the 2nd etching work procedure at this.
In the 2nd etching work procedure, velocity of flow adjust adopts mixed mode with gas supply part 60.About action and treatment conditions in addition, preferably identical with the 1st etching work procedure.Therefore, with the mixed material gas (CF of the 1st etching work procedure identical component and same traffic 4+ Ar+O 2+ H 2O) in, mix from the velocity of flow adjust gas (N of velocity of flow adjust with gas supply part 60 2).Thus, the flow of unstrpped gas is increased.
With mixed unstrpped gas (CF 4+ Ar+O 2+ H 2O+N 2) import in the plasma space 43 and with its plasma.Thus, generation contains HF, COF 2Be reacted constituent and O in fluorine 3, the oxidative reaction composition such as O free radical processing gas.Below, the processing gas of the 2nd etching work procedure suitably is called " the 2nd processes gas ".The 2nd processes flow and the velocity of flow adjust gas (N of gas 2) correspondingly the flow than the processing of the 1st in the 1st etching work procedure gas is large to mix part.The 2nd fluorine of processing in the gas is reacted constituent (HF etc.) and oxidative reaction composition (O 3Deng) amount roughly identical with the 1st etching work procedure.
Process gas with the 2nd and spray from blowing unit 59, and blow to object being treated 90.Gas flow increases, but the opening degree of blowing unit 59 is constant, therefore, the 2nd process gas from blowing unit 59 blow out the 1st speed ratio the 1st etching work procedure process gas to blow out speed large.And then the 2nd processes gas flows through on the surface of object being treated 90.Gas flow has increased, but the distance (operating distance) between blowing unit 59 and the object being treated 90 is constant, and therefore, the flow velocity of the 1st processing gas of the 2nd processing gas in lip-deep velocity ratio the 1st etching work procedure of object being treated 90 is large.
According to the increase of gas flow rate, the lip-deep moisture of object being treated 90 easily disperses.Therefore, the attachment of moisture amount on the surface of object being treated 90 is less than the 1st etching work procedure, and Thickness Ratio the 1st etching work procedure of condensed layer is little.If condensed layer reduces, the etch-rate of the silicon nitride film 92 of then substrate reduces.The etch-rate of this silicon nitride reduce etch-rate that degree causes than the minimizing of the condensed layer of following silicon to reduce degree also large.Therefore, can increase etch target film 93 with respect to the selection ratio of basilar memebrane 92.In addition, the 2nd fluorine of processing in the gas is reacted constituent (HF etc.) and oxidative reaction composition (O 3Deng) amount roughly equate with the 1st etching work procedure, therefore can suppress the reduction of the etch-rate of silicon.Thus, shown in Fig. 2 (c), can with good etch-rate optionally etching remove mottled residual film 93a, what can reduce basilar memebrane 92 crosses etch quantity d.
Switching from from the 1st etching work procedure to the 2nd etching work procedure, as long as velocity of flow adjust is switched to mixed mode with gas supply part 60 from stop mode can easily carry out, for example the response than the adding rate that changes water by addition portion 32 is also good.
Then, other execution mode of the present invention is described.In the following embodiments, for the formation that repeats with the execution mode stated, give in the accompanying drawings same symbol and suitably description thereof is omitted.
The 2nd execution mode
As shown in Figure 3, in the 2nd execution mode, velocity of flow adjust is different from the 1st execution mode (Fig. 1) to the mixing position of processing gas delivery system 10 with gas.Velocity of flow adjust is not connected with the feed line 30 of the upstream side of plasma generating unit 40 with gas supply part 60, is connected with the ejection line 50 in the downstream of plasma generating unit 40.
Ejection line 50 extends from plasma space 43.The downstream of ejection line 50 is provided with blowing unit 59.The pars intermedia of ejection line 50 is connected with gas supply part 60 with velocity of flow adjust.
Velocity of flow adjust adopts stop mode with gas supply part 60 in the 1st etching work procedure.Therefore, the action of the 1st etching work procedure is identical with the 1st execution mode.
In the 2nd etching work procedure, velocity of flow adjust adopts mixed mode with gas supply part 60.In feed line 30, generate the mixed material gas (CF with the 1st etching work procedure identical component and same traffic 4+ Ar+O 2+ H 2And import plasma generating unit 40 O).Do not have mixture velocity to regulate in the mixed material gas before importing to plasma generating unit 40 and use gas.Therefore, even switch to the 2nd etching work procedure from the 1st etching work procedure, the gaseous state in plasma space 43 can not change yet, and can make discharge stability.
By carry out plasma in plasma space 43, can obtain containing fluorine is reacted constituent (HF etc.) and oxidative reaction composition (O 3Deng) processing gas.The growing amount of these reacted constituents is identical with the 1st etching work procedure.
Should process gas and export to ejection line 50.Process the velocity of flow adjust gas (N that mixes in the gas from supply unit 60 at this 2).Thus, process the flow increase of gas.Therefore, same with the 2nd etching work procedure of the 1st execution mode, can increase the gas flow rate on the object being treated 90.
The 3rd execution mode
As shown in Figure 4, to generate respectively fluorine be reacted constituent and oxidative reaction composition to the processing gas delivery system 10 of the 3rd execution mode.It is reacting gas delivery system 33 and oxidative reaction gas delivery system 35 that processing gas delivery system 10 has respectively fluorine.Fluorine is that reacting gas delivery system 33 comprises feed line 30 and plasma generating unit 40 and fluorine system ejection road 51.Feed line 30 is except being not raw material supplying section 34 is connected with oxygen, and is all identical with the 2nd execution mode (Fig. 3).Fluorine system ejection road 51 is connected with gas supply part 60 with velocity of flow adjust.Feed line 30 only is unstrpped gas (CF with fluorine 4+ Ar+H 2O) import plasma generating unit 40.Not importing oxygen in the plasma generating unit 40 is unstrpped gas.Fluorine system extends from the downstream of the plasma space 43 of plasma generating unit 40 on ejection road 51.
Oxidative reaction gas delivery system 35 comprises that oxygen is raw material supplying section 34 and plasma generating unit 44 and the oxygen system ejection road 52 different from plasma generating unit 40.
Plasma generating unit 44 has mutual opposed pair of electrodes 45,45.Opposed faces at least one party's electrode 45 is provided with solid dielectric layer (not shown).Side in these electrodes 45,45 is connected with power supply 46, and the opposing party is for electrical ground.By by power supply 46 service voltages, the space 47 between the electrode 45,45 becomes near the plasma space the atmospheric pressure.The upstream extremity of plasma space 47 is that raw material supplying section 34 links to each other with oxygen.Oxygen system extends from the downstream of the plasma space 47 of plasma generating unit 44 on ejection road 52.
Fluorine is that collaborate mutually with the ejection road 52 of oxidative reaction gas delivery system 35 on the ejection road 51 of reacting gas delivery system 33.This interflow section links to each other with common blowing unit 53.Common blowing unit 53 is relative with object being treated 90 on the support portion 20.Common blowing unit 53 can relatively move with respect to support portion 20 in mode reciprocal between the two ends of support portion 20.
In the 3rd execution mode, being in the reacting gas delivery system 33 at fluorine, is unstrpped gas (CF with fluorine 4+ Ar+H 2O) carry out plasma in plasma generating unit 40, generate that to contain fluorine be that the fluorine of reacted constituent (HF etc.) is reacting gas, and export to ejection road 51.Meanwhile, in oxidative reaction gas delivery system 35, will be that the oxygen of raw material supplying section 34 is unstrpped gas (O from oxygen 2) import in the plasma space 47 of plasma generating unit 44 and carry out plasma, generate and contain oxidative reaction composition (O 3Deng) oxidative reaction gas.With this oxidative reaction gas from plasma generating unit 44 export to the ejection road 52, with from the ejection road 51 fluorine be that reacting gas mixes.Fluorine is that to be preferably fluorine be reacting gas to the volumetric mixture ratio of reacting gas and oxidative reaction gas: oxidative reaction gas=1: 9～9: 1, more preferably fluorine is reacting gas: oxidative reaction gas=1: 2～2: 1.By mixing, can obtain containing the processing gas that fluorine is reacted constituent and oxidative reaction composition.Should process gas and be sprayed onto object being treated 90 from blowing unit 53.
In the 3rd execution mode, owing to being to be that unstrpped gas and oxygen are that unstrpped gas is carried out plasma in plasma generating unit 40,44 separately with fluorine, therefore can increase fully respectively growing amount that fluorine is reacted constituent and the growing amount of oxidative reaction composition.Thus, can improve the etch-rate of the silicon-containing film 93 in each etching work procedure of the 1st, the 2nd, can further shorten the processing time.
In the 3rd execution mode, velocity of flow adjust adopts stop mode with gas supply part 60 in the 1st etching work procedure, and velocity of flow adjust adopts the aspect of mixed mode in the 2nd etching work procedure with gas supply part 60, and is identical with the execution mode of having stated.Therefore, in the 2nd etching work procedure, from the velocity of flow adjust gas (N of supply unit 60 2) be imported into ejection road 51, be that reacting gas mixes with fluorine.
The 4th execution mode
As shown in Figure 5, in the 4th execution mode, as the generating apparatus of the oxidative reaction gas in the oxidative reaction gas delivery system 35, can replace plasma generating unit 44 with ozone generator 48.Be the oxygen (O of raw material supplying section 34 from oxygen 2) be imported in the ozone generator 48, generate and contain O 3Oxidative reaction gas, this oxidative reaction gas be exported to the ejection road 52.
Other formation and action are identical with the 3rd execution mode (Fig. 4).
The 5th execution mode
As shown in Figure 6, the Etaching device 1 of the 5th execution mode has a plurality of (2) processing gas delivery system 10.The body delivery system 10 of regulating the flow of vital energy everywhere has the formation roughly the same with the processing gas delivery system 10 of the 1st, the 2nd execution mode (Fig. 1, Fig. 3).In order to distinguish 2 delivery systems 10, the identical symbol of inscape corresponding in the processing gas delivery system 10 for the 1st each inscape of processing gas delivery system 10A and the execution mode of having stated adopts A, the corresponding identical symbol employing B of inscape in the processing gas delivery system 10 for each inscape of the 2nd processing gas delivery system 10B and the execution mode of having stated.
The 1st process the processing gas delivery system 10 of gas delivery system 10A and the 1st, the 2nd execution mode (Fig. 1, Fig. 3) different be not to be connected with gas supply part 60 with velocity of flow adjust.Therefore, processing gas delivery system 10A from the 1st often sprays and does not contain velocity of flow adjust with gas (N 2) the 1st process gas.The 1st processing gas of processing from the 1st of delivery system 10A in the 1st etching work procedure of the composition of gas and flow and the 1st, the 2nd execution mode is identical.
The 2nd processes gas delivery system 10B has identical formation with the processing gas delivery system 10 of the 2nd execution mode (Fig. 3).Wherein, the 2nd velocity of flow adjust of processing gas delivery system 10B turns round with mixed mode often with gas supply part 60B.Therefore, processing gas delivery system 10B from the 2nd often sprays and contains velocity of flow adjust with gas (N 2) the 2nd process gas.The 2nd processing gas of processing from the 2nd of this delivery system 10B in the 2nd etching work procedure of the composition of gas and flow and the 1st, the 2nd execution mode is identical.
The amount that the ejection flow of the 1st processing gas delivery system 10A and unmixed velocity of flow adjust are used gas is less accordingly, and the 2nd ejection flow and the velocity of flow adjust of processing gas delivery system 10B uses the combined amount of gas relatively large accordingly.On the other hand, the opening degree of the blowing unit 59A of the opening degree of the blowing unit 59A of the 1st processing gas delivery system 10A and the 2nd processing gas delivery system 10B equates.Therefore, from the 1st process gas delivery system 10A blow out the flow velocity less.From the 2nd process gas delivery system 10A to blow out flow velocity relatively large.
Support portion 20 is connected with travel mechanism 22.Although omitted detailed diagram, travel mechanism 22 has such as the drive division such as engine with according to the sliding part of these drive division advance and retreat, and sliding part is connected with support portion 20.According to travel mechanism 22, support portion 20 and the 1st process gas opposed the 1st position of blowing unit 59A (solid line of Fig. 6) and and the 2nd process between opposed the 2nd position of blowing unit 59A (double dot dash line of Fig. 6) of gas mobile.
In the 1st etching work procedure, travel mechanism 22 makes support portion 20 be positioned at the 1st position.Thus, contact with object being treated 90 from the 1st the 1st processing gas of processing gas delivery system 10A ejection.Ejection flow velocity and then the flow velocity on object being treated 90 of the 1st processing gas are smaller.Therefore, easily form the condensed layer of the water of suitable thickness on the surface of object being treated 90, can improve the etch-rate of silicon-containing film 93.
In the most of etched moment of silicon-containing film 93, travel mechanism 22 makes support portion 20 from the 1st position movement to the 2 positions.Thus, switch to hardly spended time of the 2nd etching work procedure from the 1st etching work procedure.In the 2nd etching work procedure, contact with object being treated 90 from the 2nd the 2nd processing gas of processing gas delivery system 10B ejection.
The gas flow rate that the ejection flow velocity of the 2nd processing gas and then the velocity ratio on object being treated 90 the above-mentioned the 1st are processed gas delivery system 10A is large.Therefore, moisture is dispersed from the surface of object being treated 90, thereby can be suppressed at the condensed layer of the surface formation water of object being treated 90.Thus, silicon is increased with respect to the selection ratio of silicon nitride, thereby can suppress the etching of crossing of basilar memebrane 92, and optionally residual film 93a be carried out etching.
Travel mechanism 22 consists of optionally, and hand-off process gas blows the processing gas delivery system 10A that is attached to object being treated 90, the switching mechanism of 10B.
The number of the processing gas delivery system 10 that uses in the translational speed of support portion 20 or the 1st etching work procedure, the mode that can expose according to basilar memebrane 92 in the 1st etching work procedure by experiment in advance perhaps makes the minimum mode of thickness of the silicon-containing film 93 that remains on the basilar memebrane 92 determine.
Travel mechanism 22 can be connected to replace support portion 20 with blowing unit 59A, 59B, also can replace support portion 20 being moved between the 1st position and the 2nd position and blowing unit 59A, 59B being moved, in the 1st etching work procedure, make thus blowing unit 59A and support portion 20 opposed, in the 2nd etching work procedure, make blowing unit 59B and support portion 20 opposed.
The 6th execution mode
As shown in Figure 7, in the 6th execution mode, object being treated 94 is continuous sheet.The object being treated 94 of sheet is exported from conveying roller 23 continuously, and is wound roller 24 coilings.The inboard of the object being treated 94 between roller 23,24 is provided with heating part 21.
The position configuration of the close conveying roller 23 between the roller 23,24 has the blowing unit 59A of the 1st processing gas delivery system 10A.The position configuration of the close take up roll 24 between the roller 23,24 has the blowing unit 59B of the 2nd processing gas delivery system 10B.
From the object being treated 94 of conveying roller 23 output with from the 1st process the low discharge of gas delivery system 10A, the 1st processing gas of low speed contacts.Then, with from the large flow of the 2nd processing gas delivery system 10B, the 2nd processing gas of high speed contact.Thus, can travel to continuously the 2nd etching work procedure from the 1st etching work procedure.Conveying roller 23 and take up roll 24 replace the support portion 20 of objective table shape and take on the function of object being treated support portion.And conveying roller 23 and take up roll 24 consist of optionally that hand-off process gas is blown the processing gas delivery system 10A that is attached to object being treated 90, the switching mechanism of 10B.
The 7th execution mode
Process the flow of gas and then the change of flow velocity and be not limited to 2 stages, can carry out 3 more than the stage.Can change gas flow and then flow velocity more than the stage through 2 in the 1st etching work procedure.Also can change gas flow and then flow velocity more than the stage through 2 in the 2nd etching work procedure.
Fig. 8 represents that the 1st etching work procedure and the 2nd etching work procedure are altogether through the flow of 3 stage change processing gases and then the execution mode of flow velocity.
Etaching device 1 has 3 and processes gas delivery system 10.Process gas delivery system 10 in order mutually to distinguish these 3, adopt X for the processing gas delivery system 10 of phase I (being the left side among Fig. 8) and the symbol of inscape thereof, adopt Y for the processing gas delivery system 10 of second stage (being central authorities among Fig. 8) and the symbol of inscape thereof, adopt Z for the processing gas delivery system 10 of phase III (being the right side among Fig. 8) and the symbol of inscape thereof.Processing gas delivery system 10X, the 10Y of phase I and second stage processes the gas delivery system for implementing the 1st of the 1st etching work procedure.The processing gas delivery system 10Z of terminal stage (phase III) processes the gas delivery system for implementing the 2nd of the 2nd etching work procedure.
The processing gas delivery system 10X of phase I processes gas delivery system 10A with the 1st of the 5th execution mode (Fig. 6) and the 6th execution mode (Fig. 7) and has identical formation.That is, processing gas delivery system 10X is not connected with gas supply part 60 with velocity of flow adjust.Do not contain velocity of flow adjust gas (N from the 1st processing gas of processing gas delivery system 10A ejection 2), be low discharge.
The processing gas delivery system 10Y of second stage processes gas delivery system 10B with the 2nd of the 5th, the 6th execution mode (Fig. 6, Fig. 7) and has identical formation, and velocity of flow adjust turns round with mixed mode often with gas supply part 60Y.Wherein, velocity of flow adjust uses the mixed traffic of gas little with the mixed traffic of gas than the above-mentioned the 2nd velocity of flow adjust of processing gas delivery system 10B.
The processing gas delivery system 10Z of phase III (terminal stage) has the formation identical with the 2nd processing gas delivery system 10B of the 5th, the 6th execution mode (Fig. 6, Fig. 7), and velocity of flow adjust turns round with mixed mode often with gas supply part 60Y.Velocity of flow adjust is also identical with above-mentioned the 2nd processing gas delivery system 10B with the mixed traffic of gas.
Be preferably based on the velocity of flow adjust of second stage with the mixed traffic of gas 1 times～4 times of the velocity of flow adjust of gas supply part 60Y, more preferably 2 times～3 times with the mixed traffic of gas with the velocity of flow adjust of gas supply part 60Z based on the velocity of flow adjust of phase III.
Therefore, the ejection flow of processing gas is really large in the processing gas delivery system 10 of after-stage.
3 blowing units 59 of processing gas delivery system 10 are in line across the interval.The below of these blowing units 59 is provided with roller path 25.Roller path 25 extends setting in the orientation of blowing unit 59.Utilize roller path 25, object being treated 90 is transferred with the order of the below of the below of the blowing unit 59Y of the below of the blowing unit 59X of phase I, second stage, the blowing unit 59Z of phase III.
Roller path 25 consists of conveying mechanism and the supporting mechanism of object being treated 90.And roller path 25 consists of the switching mechanism that hand-off process gas optionally blows the processing gas delivery system 10 that is attached to object being treated 90.
The number of the translational speed of roller path 25 or processing gas delivery system 10 is determined according to experiment in advance.
[the 1st etching work procedure]
Object being treated 90 is along with the conveying that utilizes roller path 25, at first contacts with processing gas from the processing gas delivery system 10X of phase I, so that etched.Unmixed velocity of flow adjust gas (N in the processing gas of phase I 2), the gas flow rate on the object being treated 90 is less.Therefore, can form on the surface of object being treated 90 condensed layer of needed abundant thickness, carry out etching silicon 93 with high etch rates.In the etching of phase I, the surperficial roughening of silicon-containing film 93 and be the state of convex-concave.The silicon nitride film 92 of substrate not yet exposes.
Then, object being treated 90 contacts with processing gas from the processing gas delivery system 10Y of second stage, and then etched.In the processing gas of second stage, be mixed with velocity of flow adjust gas (N 2).Therefore, the flow-rate ratio phase I of the processing gas of second stage is large, and the gas flow rate on the object being treated 90 is larger than the phase I.Thus, moisture is dispersed from the surface of object being treated 90, can make the Thickness Ratio of lip-deep condensed layer of object being treated 90 little during the phase I.Thereby, can increase silicon-containing film 93 with respect to the selection ratio of basilar memebrane 92.Therefore, when the concave portion of the convex-concave surface that arrives silicon-containing film 93 and the interface between the basilar memebrane 92, can suppress basilar memebrane 92 and be cut down.
[the 2nd etching work procedure]
Then, object being treated 90 contacts with processing gas from the processing gas delivery system 10Z of phase III (terminal stage), and then etched.In the processing gas of phase III, be mixed with than the more velocity of flow adjust of second stage (final stage of the 1st etching work procedure) amount gas (N 2).Therefore, the flow-rate ratio second stage of the processing gas of phase III is larger, and the gas flow rate on the object being treated 90 is larger than second stage.Thus, moisture is dispersed fully from the surface of object being treated 90, less when making the Thickness Ratio second stage of lip-deep condensed layer of object being treated 90.Thereby, can further increase silicon-containing film 93 with respect to the selection ratio of basilar memebrane 92.The excessively etch quantity d (Fig. 2 (d)) of basilar memebrane 92 can be fully reduced, mottled residual film 93a can be removed reliably simultaneously.
The 8th execution mode
Fig. 9 shows the 8th execution mode of the present invention.In the 8th execution mode, oxidative reaction gas is substituted as velocity of flow adjust gas.
Particularly, the processing gas delivery system 10 of the 8th execution mode and the 4th execution mode (Fig. 5) are same, comprise that fluorine is reacting gas delivery system 33 and the oxidative reaction gas delivery system 35 with ozone generator 48.Fluorine is that reacting gas delivery system 33 is different from the 4th execution mode, is not connected with gas supply part 60 with velocity of flow adjust as flow adjustment mechanism.Instead, be on the line of raw material supplying section 34 and ozone generator 48 at the oxygen that links oxidative reaction gas delivery system 35, be provided with the oxidative reaction gas flow adjusting portion 61 as flow adjustment mechanism.Flow control division 61 is made of flow control valve or mass flow controller.61 pairs of flow control divisions are that the oxygen that raw material supplying section 34 supplies with to ozone generator 48 is unstrpped gas (O from oxygen 2) flow regulate, and then to the oxidative reaction gas (O from ozone generator 48 2+ O 3) the supply gas flow regulate.
Also flow control division 61 can be arranged on the ejection road 52 in the downstream of ozone generator 48.
[the 1st etching work procedure]
The 1st etching work procedure of the 8th execution mode is identical in fact with the 1st etching work procedure of the 3rd and the 4th execution mode.Being in the reacting gas delivery system 33 at fluorine, is unstrpped gas (CF with the humidification fluorine 4+ Ar+H 2O) carry out plasma, generating fluorine is reacting gas.With its simultaneously, be that raw material supplying section 34 is unstrpped gas (O with oxygen from the oxygen of oxidative reaction gas delivery system 35 2) be supplied in ozone generator 48, utilize ozone generator 48 to generate oxidative reaction gas (O 2+ O 3).Be that reacting gas and oxidative reaction gas are mixed to get processing gas again with these fluorine.Should process gas from blowing unit 53 ejections, and contact with object being treated 90.Fluorine in the 1st etching work procedure be the volumetric mixture ratio preference of reacting gas and oxidative reaction gas as being reacting gas for fluorine: oxidative reaction gas=2: 1～about 1: 2.
[the 2nd etching work procedure]
In the 2nd etching work procedure of the 8th execution mode, making oxygen by flow control division 61 is unstrpped gas (O 2) and then oxidative reaction gas (O 2+ O 3) supply flow rate larger than the 1st etching work procedure.Fluorine is that the supply flow rate of reacting gas is preferably identical with the 1st etching work procedure.Fluorine in the 2nd etching work procedure be the mixing ratio preference of reacting gas and oxidative reaction gas as being reacting gas for fluorine: oxidative reaction gas=9: 5～about 1: 3, about more preferably 1: 1～1: 2.
Increase by the flow that makes oxidative reaction gas, the flow of processing gas integral body is increased.Thus, processing the flow velocity of gas on object being treated 90 increases.Therefore, object being treated 90 lip-deep moisture become and easily disperse.Thereby, same with the 1st execution mode, can increase silicon fiml 93 with respect to the selection ratio of basilar memebrane 92.For fluorine is reacting gas, by being set as the flow identical with the 1st etching work procedure, can suppress the reduction of the etch-rate of silicon.Consequently, can be with the residual film 93a of silicon with good etch-rate and optionally carry out etching and remove, and can reduce basilar memebrane 92 cross etch quantity d.
In the 8th execution mode, oxidative reaction gas doubles as velocity of flow adjust gas, therefore, need not the gas (N for example of velocity of flow adjust special use 2).Therefore, can reduce the kind of desired gas.
The present invention is not limited to above-mentioned execution mode, can carry out various changes in the apparent scope of the art personnel.
For example, be not limited to unformed silicon as the silicon-containing film 93 of etch target, can be polysilicon, also can be monocrystalline silicon.
Silicon-containing film 93 as etch target is not limited to silicon, also can be silica, carborundum, silicon oxide carbide etc.
When being silica as the silicon-containing film 93 of etch target, processing gas and there is no need to contain the oxidative reaction composition.Therefore, can omit oxygen is raw material supplying section 34.
When being carborundum or silicon oxide carbide as the silicon-containing film 93 of etch target, can being converted into silicon by heating operation, and then similarly carrying out etching with above-mentioned execution mode.
Basilar memebrane 92 is not limited to silicon nitride, so long as from get final product as the different composition of the silicon-containing film 93 of etch target.
When silicon-containing film 93 was made of silicon such as unformed silicon, basilar memebrane 92 can be silica.
When being silica as the silicon-containing film 93 of etch target, basilar memebrane can be for example silicon nitride.
When being carborundum or silicon oxide carbide as the silicon-containing film 93 of etch target, basilar memebrane 92 can be for example silicon nitride or silica.
Because the impact of substrate constituent of the film etc. is carried out along with etched, silicon becomes large with respect to the selection of basilar memebrane than meeting, therefore can reduce the processing gas flow rate on object being treated 90.Also can make the processing gas flow rate in the 2nd etching work procedure less than the 1st etching work procedure.After reducing to process gas flow rate, also can increase.After increasing the processing gas flow rate, also can reduce.Be not limited to make the processing gas flow rate to change interimly, also change serially (reducing gradually or gradually increase).
When velocity of flow adjust is mixed mode with gas supply part 60, can or make continuously velocity of flow adjust gas (N interimly 2) mixed traffic change.
Flow adjustment mechanism can replace mixture velocity adjusting gas (N in processing gas delivery system 10 for the flow velocity of processing gas is changed 2), perhaps regulate with gas (N at mixture velocity 2) the basis on, making fluorine is unstrpped gas (CF 4+ Ar) flow changes, or to make fluorine be that the flow of the diluent gas (Ar) in the unstrpped gas changes, or to make oxygen be raw material (O 2) flow change.
Flow adjustment mechanism can replace adjusting gas flow for the flow velocity of processing gas is changed, and perhaps on the basis of adjusting gas flow, regulates the opening degree of blowing unit 59.Also can regulate the thickness (distance between blowing unit 59 and the object being treated 90) on the gas road that forms between blowing unit 59 and the object being treated 90.
Be raw material as fluorine, can replace CF 4, use C 2F 6, C 3F 6, C 3F 8Deng other PFC (perfluorocarbon), also can use CHF 3, CH 2F 2, CH 3The HFC such as F (HFC) also can use SF 6, NF 3, XeF 2Deng the fluorochemical beyond PFC and the HFC.
As diluent gas, can replace Ar, use He, Ne, N 2Deng other inert gas.
Be raw material as oxygen, can replace O 2, use NO, NO 2, N 2The oxygenatedchemicalss such as O.
Also can replace water (H 2O) use the compound that contains the OH base.As the compound that contains the OH base, can enumerate aquae hydrogenii dioxidi (H 2O 2) or the alcohol such as ethanol or methyl alcohol.But, for aquae hydrogenii dioxidi, because its reactivity is high, be difficult to stably be added in the gas that fluorine is reacted constituent.In addition, for alcohol, carbon component (C) reacts when importing in the plasma, generates organic polymer, therefore needs to decompose and removes.The H that therefore, preferably can supply with in easy and stable mode 2O.
Also can replace using plasma generating unit 44 or ozone generator 48 to generate the oxidative reaction composition, and with O 3Be accumulated in advance in the groove and from this groove, take out the oxidative reaction composition and be that reacted constituent mixes with fluorine Deng the oxidative reaction composition.
In the 3rd execution mode (Fig. 4) and the 4th execution mode (Fig. 5), also can not to be reacting gas with fluorine mix from oxidative reaction gas and blow to object being treated from different respectively blowing units.
The moment that switches to the 2nd etching work procedure from the 1st etching work procedure is not limited to the stage that basilar memebrane 92 exposes, and also can be set in the stage that basilar memebrane 92 exposes last short time.
A plurality of processing gas delivery systems 10 are being set, optionally switch in the situation with object being treated 90 opposed systems 10 with switching mechanism, process gas delivery system 10 and be not limited to 2 (the 5th, the 6th execution mode (Fig. 6, Fig. 7)) or 3 (the 7th execution mode (Fig. 8)), also can set more than 4.
At least 2 gas flow and then flow velocitys of processing gas delivery system 10 in a plurality of processing gas delivery systems 10 can be different, it is all not identical that all gas flow of a plurality of processing gas delivery systems 10 and then flow velocity are not limited to every one-phase, and gas flow and then the flow velocity of the processing gas delivery system 10 of the part (more than 2) in a plurality of (more than 3) processing gas delivery system 10 also can be identical.
In the 7th execution mode (Fig. 8), arrange simultaneously 2 and process gas delivery system 10X, process gas delivery system 10 4 of device 1 whole installations.This structure is large at the thickness of silicon-containing film 93, preferred in half a situation of processing among the gas delivery system 10X thickness that can etched quantity not sufficient silicon-containing film 93.That is, process gas delivery system 10X by arranging 2, can be with good etch-rate etching over half even most silicon-containing film 93.Then, the selection ratio that increases silicon in processing gas delivery system 10Y carries out etching, and then, the selection ratio that further increases silicon in processing gas delivery system 10Z carries out etching.
Also can according to the thickness of silicon-containing film 93, arrange simultaneously and process gas delivery system 10X more than 3.
In the 7th execution mode (Fig. 8), velocity of flow adjust gas supply part 60 can be set in the processing gas delivery system 10X of phase I also.
Also a plurality of execution modes can be made up mutually.For example, (velocity of flow adjust of Fig. 4～Fig. 8) is connected with feed line 30 with gas supply part 60 and the 1st execution mode (Fig. 1) equally with the 3rd～the 7th execution mode.
(the body delivery system 10 of regulating the flow of vital energy everywhere of Fig. 6～Fig. 8) also can be for same with the 3rd, the 4th execution mode (Fig. 4, Fig. 5), and fluorine is reacted constituent and the formation of oxidative reaction composition with mutually different approach generation for the 5th～the 7th execution mode.
In the 8th execution mode (Fig. 9), can replace ozone generator 48, and use the plasma generating unit 44 of the 3rd execution mode (Fig. 4).
In the 1st, the 2nd execution mode (Fig. 1, Fig. 2), also can be same with the 8th execution mode, omit velocity of flow adjust gas supply part 60, instead of the link road that at oxygen is raw material supplying section 34 and feed line 30 flow control division 61 being set, is that unstrpped gas and then oxidative reaction composition substitute as velocity of flow adjust gas with oxygen.At this moment, be careful along with oxygen is the changes in flow rate of unstrpped gas, and the stability of the discharge of plasma generating unit 40 and fluorine are the impact that the formation efficiency of reacting gas brings.
In the 5th, the 6th execution mode (Fig. 6, Fig. 7), also can be same with the 8th execution mode, omit the velocity of flow adjust gas supply part 60B that processes gas delivery system 10B, instead of the link road that at oxygen is the 34B of raw material supplying section and feed line 30B flow control division 61 being set, is that unstrpped gas and then oxidative reaction composition substitute as velocity of flow adjust gas with oxygen.At this moment, be careful and be accompanied by the changes in flow rate that oxygen is unstrpped gas, the impact that the formation efficiency that the stability of the discharge among the plasma generating unit 40B and fluorine are reacting gas brings.
In the 7th execution mode (Fig. 8), also can be same with the 8th execution mode, omit the velocity of flow adjust gas supply part 60Y, the 60Z that process gas delivery system 10Y, 10Z, being replaced by at oxygen is that each link road of the 34Y of raw material supplying section, 34Z and feed line 30Y, 30Z arranges flow control division 61, is that unstrpped gas and then oxidative reaction composition substitute as velocity of flow adjust gas with oxygen.At this moment, be careful and be accompanied by the changes in flow rate that oxygen is unstrpped gas, the impact that the formation efficiency that the stability of the discharge of plasma generating unit 40X, 40X and fluorine are reacting gas brings.
(the body delivery system 10 of regulating the flow of vital energy everywhere of Fig. 6～Fig. 8) also can be with the 3rd, the 4th execution mode (Fig. 4, Fig. 5) same the 5th～the 7th execution mode, making fluorine is reacted constituent and the formation of oxidative reaction composition with different approach generations, and process gas delivery system 10B, 10X, 10Y and also can be with the 8th execution mode (Fig. 9) equally, the oxidative reaction composition substituted make velocity of flow adjust with the formation of gas.At this moment, how to change no matter oxygen is the flow of unstrpped gas, can guarantee the stability of the discharge among plasma generating unit 40B, 40X, the 40Y, making fluorine is that the formation efficiency of reacting gas is stable, and then can suppress the change of the etch-rate of silicon-containing film.
Engraving method of the present invention and Etaching device except can be applicable to by patternings such as resists the pattern etching carried out of object being treated, also can be applicable in the planarization and the surface of silicon chip or glass or the roughening at the back side etc. of roughening part of the removing of the siliceous pollutant that adheres on the surface of object being treated, silicon chip or glass.
Embodiment 1
Embodiment is described.The present invention is not limited to this embodiment.
Use the Etaching device of Fig. 5, unformed silicon fiml is carried out etch processes with the 1st etching work procedure and these 2 stages of the 2nd etching work procedure.Basilar memebrane is silicon nitride, uses the stacked sample of unformed silicon on this basilar memebrane.
At first, carry out the 1st etching work procedure.
Be raw material as fluorine, use CF 4As diluent gas, use Ar.With CF 4With the Ar dilution, obtaining fluorine is unstrpped gas (CF 4+ Ar).Mixing ratio is as described below.
CF 4∶Ar＝10∶90
Be unstrpped gas (CF at above-mentioned fluorine 4+ Ar) middle with commercially available moisture adding set interpolation moisture.It is 18 ℃ that amount of moisture is controlled to dew point temperature.
Velocity of flow adjust adopts stop mode with gas supply part 60.
The fluorine that will add behind the water with plasma generating unit 40 is unstrpped gas (CF 4+ Ar+H 2O) behind the plasma, obtaining fluorine is reacting gas.Plasma discharge conditions is as described below.
Interval between electrode: 1mm
Inter-electrode voltage: 12kV
Supply frequency: 40kHz (impulse wave)
In addition, be unstrpped gas as oxygen, with O 2Gas imports in the ozone generator 48 and obtains oxidative reaction gas (O 2+ O 3).The ozone concentration of oxidative reaction gas is approximately 8%.
To be reacting gas from the fluorine of plasma generating unit 40 mixes with oxidative reaction gas from plasma generating unit 44, obtains the 1st and processes gas.Fluorine is that the volumetric mixture ratio of reacting gas and oxidative reaction gas is 1: 1.
Object being treated 90 is placed on the objective table 20, configures above it blowing unit 53.Blow out the 1st from blowing unit 53 and process gas, meanwhile make blowing unit 53 to move (scanning) in an end to the mode reciprocal between the other end from object being treated 90.Translational speed is 4m/min.The one way of the direction of going or the direction of returning is moved as 1 scanning, carry out 18 scanning, finish the 1st etching work procedure.At this moment, at the remained on surface of object being treated 90 the mottled unformed silicon 93a of 0.1～10 μ m (with reference to Fig. 2 (b) (c)).
The etch-rate of the unformed silicon fiml of the 1st etching work procedure is 10.1nm/scan, unformed silicon fiml with respect to the selection of silicon nitride film than being approximately 1.3.
Then, carry out the 2nd etching work procedure.In the 2nd etching work procedure, velocity of flow adjust adopts mixed mode with gas supply part 60.Fluorine is reacting gas and velocity of flow adjust gas (N 2) between mixing ratio be that fluorine is reacting gas: velocity of flow adjust was with gas=2: 3.The scanning times of blowing unit 53 is 4 times.The treatment conditions of other in the 2nd etching work procedure are identical with the 1st etching work procedure.
Can fully remove residual unformed silicon 93a by the 2nd etching work procedure.
The etch-rate of the unformed silicon fiml of the 2nd etching work procedure is 8.6nm/scan, and frequently the 1st etching work procedure is high with respect to the selection of silicon nitride film for unformed silicon fiml, is about 2.3.Therefore, confirm the excessively etching of the silicon nitride film 92 that can reduce substrate.
Embodiment 2
Investigate velocity of flow adjust with gas and process gas mixing ratio, and unformed silicon with respect to the selection of silicon nitride than between relation.Use similarly to Example 1 the Etaching device of Fig. 5.Material composition and the formation condition of processing gas are identical with embodiment 1.In this processing gas, mix as the nitrogen (N of velocity of flow adjust with gas 2), and the mixed traffic of nitrogen is changed.Measure the etch-rate of unformed silicon (a-Si) and silicon nitride (SiNx), calculate unformed silicon (a-Si) with respect to the selection ratio of silicon nitride (SiNx).
The result as shown in figure 10.As shown in figure 10, along with velocity of flow adjust gas (N 2) mixing ratio increase, the etch-rate of the etch-rate of unformed silicon (a-Si) and silicon nitride (SiNx) all reduces, but the reduction degree of the etch-rate of silicon nitride (SiNx) is larger than unformed silicon (a-Si).Therefore, along with velocity of flow adjust gas (N 2) mixing ratio increase, unformed silicon (a-Si) with respect to the selection of silicon nitride (SiNx) than increasing.By this result as can be known, in the 2nd etching work procedure, thereby the velocity of flow adjust that mixes suitable amount in processing gas increases its flow velocity with gas, can suppress the etching of crossing of silicon nitride film 92.
Embodiment 3
Investigate to use the Etaching device of Fig. 9, velocity of flow adjust substituted in the situation into oxidative reaction gas with gas, oxidative reaction gas and fluorine be reacting gas mixing ratio, and unformed silicon with respect to the selection of silicon nitride than between relation.
Fluorine is that material composition and the formation condition of reacting gas is identical with embodiment 1.Wherein, embodiment 3 is different from embodiment 1, does not use as the N of velocity of flow adjust with gas 2Gas.In addition, generate by the gas (O that contains ozone by ozone generator 48 similarly to Example 1 2+ O 3) the oxidative reaction gas that consists of.Be the volumetric mixture ratio of reacting gas and oxidative reaction gas makes oxidative reaction gas as 2: 1～1: 2 mode changes in flow rate take fluorine.Fluorine is that the flow of reacting gas is constant.Measure the etch-rate of unformed silicon (a-Si) and silicon nitride (SiNx), calculate unformed silicon (a-Si) with respect to the selection ratio of silicon nitride (SiNx).
The result as shown in figure 11.As shown in figure 11, mixing ratio increase along with oxidative reaction gas, the etch-rate of the etch-rate of unformed silicon (a-Si) and silicon nitride (SiNx) all reduces, but the reduction degree of the etch-rate of silicon nitride (SiNx) is greater than unformed silicon (a-Si).Therefore, along with the mixing ratio increase of oxidative reaction gas, unformed silicon (a-Si) increases with respect to the selection ratio of silicon nitride (SiNx).Can be confirmed by this result, by in the 2nd etching work procedure, the flow of oxidative reaction gas be increased, the flow velocity of processing gas is increased, can suppress the etching of crossing of silicon nitride film 92.
Utilizability on the industry
In the manufacturing of the present invention applicable to for example flat-panel monitor (FPD) or semiconductor wafer.

Claims (16)

1. the Etaching device of a silicon-containing film is that the object being treated to stacked silicon-containing film on the basilar memebrane carries out etched device, it is characterized in that having:
The processing gas that will contain fluorine and be reacted constituent is supplied in the processing gas delivery system of described object being treated; With
Make the flow velocity of described processing gas on object being treated according to the etched flow adjustment mechanism that changes of carrying out.
2. Etaching device according to claim 1 is characterized in that,
Described flow adjustment mechanism increases described flow velocity along with etched carrying out.
3. Etaching device according to claim 1 is characterized in that,
Described flow adjustment mechanism increases described flow velocity interimly along with etched carrying out.
4. Etaching device according to claim 1 is characterized in that,
Described flow adjustment mechanism makes described flow velocity relatively large when the silicon-containing film of etch residue until make described flow velocity less most of etched in the etched part wanted of described silicon-containing film.
5. Etaching device according to claim 1 is characterized in that,
Described flow adjustment mechanism is regulated the flow of described processing gas.
6. Etaching device according to claim 1 is characterized in that,
Described processing gas delivery system comprises:
Form near the plasma generating unit of the plasma space of atmospheric pressure; With
Be that the fluorine that contains of reacted constituent is that raw material and the fluorine that added H2O or contained the compound of OH base are the feed line that unstrpped gas imports described plasma space with becoming described fluorine,
Wherein, described flow adjustment mechanism mixture velocity in described feed line is regulated with gas or is stopped to mix, and according to the Flow-rate adjustment described flow velocity of this velocity of flow adjust with gas.
7. Etaching device according to claim 1 is characterized in that,
Described processing gas delivery system comprises:
Form near the plasma generating unit of the plasma space of atmospheric pressure; With
Be that the fluorine that contains of reacted constituent is that raw material and the fluorine that added H2O or contained the compound of OH base are the feed line that unstrpped gas imports described plasma space with becoming described fluorine,
Wherein, described flow adjustment mechanism mixture velocity in the processing gas delivery system in the downstream of described plasma space is regulated with gas or is stopped to mix, and according to the Flow-rate adjustment described flow velocity of this velocity of flow adjust with gas.
8. Etaching device according to claim 5 is characterized in that,
Described processing gas delivery system comprises:
The fluorine that will contain described fluorine and be reacted constituent is that the fluorine that reacting gas is supplied in described object being treated is the reacting gas delivery system; With
The oxidative reaction gas that will contain the oxidative reaction composition is supplied in the oxidative reaction gas delivery system of described object being treated,
Wherein, described flow adjustment mechanism is regulated the supply gas flow of described oxidative reaction gas delivery system.
9. the Etaching device of a silicon-containing film is that the object being treated to stacked silicon-containing film on the basilar memebrane carries out etched device, it is characterized in that, comprising:
A plurality of processing gas delivery systems, its ejection contain the processing gas that fluorine is reacted constituent; With
Switching mechanism, it will be processed gas and blow the processing gas delivery system that is attached to described object being treated according to etched optionally the switching,
Wherein, blown when being attached to object being treated from least 2 in the described a plurality of processing gas delivery systems processing gases of processing the gas delivery systems, the flow velocity on object being treated is different.
10. Etaching device according to claim 9 is characterized in that,
Described switching mechanism is selected along with the etched relatively large processing gas delivery system of described flow velocity that carries out.
11. Etaching device according to claim 9 is characterized in that,
Described switching mechanism is until at the most of etched processing gas delivery system of selecting described flow velocity less in the etched part wanted of described silicon-containing film, select the relatively large processing gas delivery system of described flow velocity when the silicon-containing film of etch residue.
12. Etaching device according to claim 9 is characterized in that,
The flow of the processing gas of at least 2 processing gas delivery systems in described a plurality of processing gas delivery system is different.
13. Etaching device according to claim 9 is characterized in that,
The body delivery system of regulating the flow of vital energy everywhere comprises:
Form near the plasma generating unit of the plasma space of atmospheric pressure; With
Be that the fluorine that contains of reacted constituent is that raw material and the fluorine that added H2O or contained the compound of OH base are the feed line that unstrpped gas imports described plasma space with becoming described fluorine,
Wherein, the feed line of at least one processing gas delivery system is connected with gas supply part with the velocity of flow adjust that makes velocity of flow adjust with the gas interflow.
14. Etaching device according to claim 9 is characterized in that,
The body delivery system of regulating the flow of vital energy everywhere comprises:
Form near the plasma generating unit of the plasma space of atmospheric pressure; With
Be that the fluorine that contains of reacted constituent is that raw material and the fluorine that added H2O or contained the compound of OH base are the feed line that unstrpped gas imports described plasma space with becoming described fluorine,
Wherein, the processing gas delivery system in the downstream of the described plasma space of at least one processing gas delivery system is connected with gas supply part with the velocity of flow adjust that makes velocity of flow adjust with the gas interflow.
15. according to claim 6, each described Etaching device in 7,13,14, it is characterized in that,
Described velocity of flow adjust gas is inert gas.
16. according to claim 6, each described Etaching device in 7,13,14, it is characterized in that,
Described velocity of flow adjust gas is oxidative reaction gas.
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