CN104944364B - Silica release process - Google Patents

Silica release process Download PDF

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CN104944364B
CN104944364B CN201410117472.5A CN201410117472A CN104944364B CN 104944364 B CN104944364 B CN 104944364B CN 201410117472 A CN201410117472 A CN 201410117472A CN 104944364 B CN104944364 B CN 104944364B
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gas
passed
release process
content
process cavity
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CN104944364A (en
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贾照伟
王坚
王晖
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ACM (SHANGHAI) Inc
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Abstract

The present invention proposes a kind of completely new silica release process for being intended to inhibit fine structure adhesion.The silica release process includes:A. catalyzed gas is passed through into process cavity;B. HF gases are passed through into the process cavity, wherein the HF gases under the action of catalyzed gas with the silicon dioxde reaction in the process cavity;And c. is passed through F into the process cavity2Gas or XeF2Gas, with the H in the process cavity2O reacts.H is not contained in the final product of the technique of the present invention2O, thus avoid together may caused by fine structure adhesion the problem of.

Description

Silica release process
Technical field
The present invention relates to field of semiconductor processing more particularly to a kind of silica release process.
Background technology
Currently, MEMS(MEMS)The development of manufacturing process gradually appears gas phase HF etching silicon dioxides, to realize Release of some special constructions, such as cantilever beam, gyroscope and cmos device etc..
The dry release process of mainstream needs to pass first into methanol or ethyl alcohol either isopropanol or other alcohols gas Body moistens sample surfaces and in the reaction as catalyst, is passed through anhydrous HF gas and silicon dioxde reaction later.
A large amount of water can be generated in the process, aqueous vapor condenses once being formed can cause fine structure to generate adhesion, in order to It avoids subsequently generating adhesion, needs continuously to be passed through methanol gas, and this kind of alcohols gas belongs to inflammable and explosive, to life Production equipment workshop has certain danger, cost also can be relatively high.
Invention content
For the above-mentioned technical problem of the prior art, it is intended to inhibit fine structure adhesion present invention particularly provides a kind of Completely new silica release process.
Specifically, the present invention provides a kind of silica release process, including:
A. catalyzed gas is passed through into process cavity;
B. HF gases are passed through into the process cavity, wherein the HF gases are same described under the action of the catalyzed gas Silicon dioxde reaction in process cavity;And
C. it is passed through F into the process cavity2Gas or XeF2Gas, with the H in the process cavity2O reacts.
Preferably, in above-mentioned silica release process, the step b and the step c are carried out at the same time.
Preferably, in above-mentioned silica release process, the step c is carried out after the step b.
Preferably, in above-mentioned silica release process, after the step c, the silica release process Further include:D. the O in the process cavity is detected2Content;And if the O that e1. is detected2Content is kept within a predetermined period of time O default less than one2Content then terminates the silica release process.
Preferably, in above-mentioned silica release process, after the step d, the silica release process Further include:If the O e2. detected2Content does not remain less than the default O in the predetermined amount of time2Content then empties institute Process cavity is stated, the step a~step d is then repeated, until as the O detected2Content is in the predetermined amount of time Remain less than the default O2Above-mentioned steps e1 is executed when content.
Preferably, in above-mentioned silica release process, the catalyzed gas be gaseous water, ethyl alcohol, methanol or Person's isopropanol.
Preferably, in above-mentioned silica release process, the step a further comprises:It is being passed through catalyzed gas While from the gas outlet gas bleeding of the process cavity with by the vacuum pressure of the process cavity be held in 5 supports to 500 supports it Between.
Preferably, in above-mentioned silica release process, the F in the step c2Gas or XeF2Gas Intake be more than 1 with the ratio between intake of HF gases in the step b:2.
Preferably, in above-mentioned silica release process, the HF gases are anhydrous HF gas.
Preferably, in above-mentioned silica release process, before the step a or the step e1 it Afterwards, which further includes:With nitrogen to being purged inside the process cavity.
The technique of the present invention is mainly characterized by:It passes first into as the gas for starting gas and catalyst;Then, lead to Enter HF gases and silicon dioxde reaction, while being passed through HF gases or a little later when be passed through F2Or XeF2Gas, first HF It is SiF with silicon dioxde reaction product4And H2O, F2It can be with the H of generation2O reactions generate HF and O2, the HF that generates in this way can be into One step and silicon dioxde reaction improve reaction efficiency.Further, since not containing H in final product2O, therefore avoiding together can Caused by energy the problem of fine structure adhesion.In addition, the silica release process of the present invention not only has above-mentioned technical aspect The advantages of, and production cost can also be substantially reduced.
It should be appreciated that the general description and the following detailed description more than present invention is all exemplary and illustrative, And it is intended that the present invention as claimed in claim provides further explanation.
Description of the drawings
It is to provide further understanding of the invention including attached drawing, they are included and constitute part of this application, Attached drawing shows the embodiment of the present invention, and plays the role of the explanation principle of the invention together with this specification.In attached drawing:
Fig. 1 shows the method flow diagram of basic principle according to the present invention.
Fig. 2 shows the method flow diagrams of a preferred embodiment of the present invention.
Fig. 3 shows the method flow diagram of another preferred embodiment of the present invention.
Fig. 4 shows the method flow diagram of the another preferred embodiment of the present invention.
Specific implementation mode
The embodiment of the present invention is described with detailed reference to attached drawing now.Now with detailed reference to the preferred implementation of the present invention Example, its example is shown in the drawings.In the case of any possible, phase will be indicated using identical label in all the appended drawings Same or similar part.In addition, although the term used in the present invention is selected from public term, this Some terms mentioned in description of the invention may be that applicant carrys out selection by his or her judgement, and detailed meanings are at this Illustrate in the relevant portion of the description of text.In addition, it is desirable that not only by used actual terms, and be also to by each Meaning that term is contained understands the present invention.
Referring initially to Fig. 1, silica release process 100 of the invention mainly includes the following steps that:Lead into process cavity Enter catalyzed gas(Step 101);HF gases are passed through into process cavity(Step 102), preferably anhydrous HF gas, wherein the HF gas Body is under the action of the catalyzed gas with the silicon dioxde reaction in the process cavity;And it is passed through F into the process cavity2Gas or Person XeF2Gas(Step 103), with the H in the process cavity2O reacts.
In a step 101, which is gaseous water, ethyl alcohol, methanol or isopropanol, is passed through in the form of a vapor Process cavity, and adsorb on the surface of the workpiece.It is highly preferred that selecting water vapour as catalyst, to reduce cost.In order to ensure water In gas phase and realize relatively good adsorption effect.Preferably, vacuum available is pumped from the gas outlet of process cavity while ventilation Extraction, keeps the pressure of process cavity in certain vacuum pressure, and preferred vacuum pressure range is 5 supports between 500 supports.
In a step 102, the anhydrous HF gas being passed through in process cavity ionizes under the action of catalyzed gas above-mentioned And it reacts with silica.Equation is as follows:
4HF+SiO2=SiF4+2H2O (Reaction equation 1)
Assuming that reaction speed is sufficiently fast, the HF gases whole and SiO being passed through2Reaction, the amount of the water of generation is reacted HF Half.
In this way, in step 103, participating in reaction in HF and generating H2O can be with the F that is passed through2Gas or XeF2Gas occurs Reaction, for example, using F2Embodiment equation it is as follows:
2F2+2H2O==4HF+O2(Reaction equation 2)
The F consumed in reaction2It is equal with the amount of water.The HF of generation again can further with SiO2Reaction,
4HF+SiO2=SiF4+2H2O (Reaction equation 3)
F is used with this2The embodiment of gas is compared, and it is XeF to be passed through gas2Its reaction principle of embodiment and F2 embodiments It is identical, Xe gas is only increased in by-product.
It is appreciated that the ratio of the HF and generation water in above-mentioned reaction equation 1 are 2:1, so the F being passed through2Gas or XeF2The ratio of gas and HF gases is 1:2. it is contemplated that still with the presence of water in the product of reaction equation 3, if water content The more adhesion problems that still will produce fine structure, therefore more F can be passed through in the present invention2Gas or XeF2Gas.F2 Gas or XeF2The intake of gas and the gas flow of HF are preferably greater than 1:2.
The ratio of the above-mentioned gas of process cavity, after silica is depleted, by-product are passed through by reasonable disposition In water meeting and F2Reaction generates extra HF and O2, to thoroughly avoid the problem of sticking together.Finally, it is depleted in water HF and oxygen just there will be no to generate later.
In addition, according to a preferred embodiment of the present invention, can also pacify in the gas outlet of process cavity or process cavity Fill O2Detector, to judge whether release reaches terminal.For example, detecting O if continued for some time2Content be less than it is normal Technique terminates when the content value of oxygen under vacuum.
If the O detected2Content remains less than a default O within a predetermined period of time2Content(The default O2Content is preferred It is the content of oxygen under normal vacuum), then terminate the silica release process.
Fig. 2 shows the method flow diagrams of a preferred embodiment of the present invention.Embodiment shown in Fig. 2 is the same as shown in Fig. 1 Embodiment it is essentially identical, the two differs only in:In the embodiment shown in Figure 2 so that the step that the priority in Fig. 1 is implemented Rapid 102 and 103 are carried out at the same time, i.e., are passed through HF gases and F simultaneously in the step 202 of Fig. 22Gas or XeF2Gas.Remaining Identical content is referred to the above detailed description for Fig. 1, and details are not described herein again.
The method flow diagram of another preferred embodiment of the present invention is shown turning now to Fig. 3, Fig. 3.The silica is released Putting technique 300 allows the gas using pulsed to be passed through mode to improve gas utilization efficiency.The technique includes mainly following step Suddenly:Catalyzed gas is passed through into process cavity(Step 301);HF gases are passed through into process cavity(Step 302), preferably anhydrous HF Gas, wherein the HF gases are under the action of the catalyzed gas with the silicon dioxde reaction in the process cavity;And to the technique Intracavitary is passed through F2Gas or XeF2Gas(Step 303), with the H in the process cavity2O reacts;Detect the O in the process cavity2 Content(Step 304);Judge the O detected2Whether content remains less than a default O within a predetermined period of time2Content(Step 305);If so, terminating the silica release process(Step 306);If it is not, then emptying the process cavity(Step 307), then The step 301~step 304 is repeated, until as the O detected2It is default that content remains less than this in the predetermined amount of time O2Above-mentioned steps 306 are executed when content.
In step 301, which is gaseous water, ethyl alcohol, methanol or isopropanol, is passed through in the form of a vapor Process cavity, and adsorb on the surface of the workpiece.It is highly preferred that selecting water vapour as catalyst, to reduce cost.In order to ensure water In gas phase and realize relatively good adsorption effect.Preferably, can be controlled by the pressure or flow controller of process cavity Make the gas flow being passed through.
In step 302, the anhydrous HF gas being passed through in process cavity ionizes under the action of catalyzed gas above-mentioned And it reacts with silica.Equation is as follows:
4HF+SiO2=SiF4+2H2O (Reaction equation 1)
Assuming that reaction speed is sufficiently fast, the HF gases whole and SiO being passed through2Reaction, the amount of the water of generation is reacted HF Half.Preferably, in this step, the gas being passed through can also be controlled by the pressure or flow controller of process cavity Amount.
In this way, in step 303, participating in reaction in HF and generating H2O can be with the F that is passed through2Gas or XeF2Gas occurs Reaction, for example, using F2Embodiment equation it is as follows:
2F2+2H2O==4HF+O2(Reaction equation 2)
The F consumed in reaction2It is equal with the amount of water.The HF of generation again can further with SiO2Reaction,
4HF+SiO2=SiF4+2H2O (Reaction equation 3)
F is used with this2The embodiment of gas is compared, and it is XeF to be passed through gas2Its reaction principle of embodiment and F2 embodiments It is identical, Xe gas is only increased in by-product.
It is appreciated that the ratio of the HF and generation water in above-mentioned reaction equation 1 are 2:1, so the F being passed through2Gas or XeF2The ratio of gas and HF gases is 1:2. it is contemplated that still with the presence of water in the product of reaction equation 3, if water content The more adhesion problems that still will produce fine structure, therefore more F can be passed through in the present invention2Gas or XeF2Gas.F2 Gas or XeF2The intake of gas and the gas flow of HF are preferably greater than 1:2.
In step 304, O can be installed in the gas outlet of process cavity or process cavity2Detector, to detect the technique The O of intracavitary2Content.Then, in step 305, judge the O detected2It is pre- whether content remains less than one within a predetermined period of time If O2Content(The default O2Content is preferably the content of oxygen under normal vacuum).If it is(That is, detecting in process cavity Without O2), then illustrate that the technique has terminated(Step 306).If it is not, then at this moment can be with exhaust process chamber(Step 307), example The gas and by-product in process cavity can such as be taken away with vacuum pump.Then, above-mentioned etch step is repeated(That is step 301- steps 304), the condition that terminates until meeting technique.
Fig. 4 shows the method flow diagram of a preferred embodiment of the present invention.Embodiment shown in Fig. 4 is the same as shown in Fig. 3 Embodiment it is essentially identical, the two differs only in:In the embodiment shown in fig. 4 so that the step that the priority in Fig. 3 is implemented Rapid 302 and 303 are carried out at the same time, i.e., are passed through HF gases and F simultaneously in the step 402 of Fig. 42Gas or XeF2Gas.Remaining Identical content is referred to the above detailed description for Fig. 3, and details are not described herein again.
The processes such as nitrogen purging are not referred in implementations described above, it generally can also be before etching starts(Such as Before step 101)After end(Such as after step 104)Increase nitrogen purge step, the gas of purging in addition to nitrogen with The inert gases such as helium, argon gas can be used outside.
In conclusion the technique of the present invention is mainly characterized by:It passes first into as the gas for starting gas and catalyst Body;Then, HF gases and silicon dioxde reaction are passed through, while being passed through HF gases or a little later when be passed through F2Or XeF2 Gas, first HF and silicon dioxde reaction product are SiF4And H2O, F2It can be with the H of generation2O reactions generate HF and O2, generate in this way HF can further with silicon dioxde reaction, improve reaction efficiency.Further, since not containing H in final product2O, therefore one And the problem of avoiding fine structure adhesion caused by possibility.In addition, the silica release process of the present invention is not only with upper The advantages of stating technical aspect, and production cost can also be substantially reduced.
Those skilled in the art can be obvious, can to the present invention the above exemplary embodiments carry out various modifications and modification and Without departing from the spirit and scope of the present invention.Accordingly, it is intended to which present invention covering is made to fall in the appended claims and its equivalence techniques Modifications of the present invention in aspects and modification.

Claims (8)

1. a kind of silica release process, which is characterized in that including:
A. catalyzed gas is passed through into process cavity, from the gas outlet gas bleeding of the process cavity while being passed through catalyzed gas The vacuum pressure of the process cavity is held in 5 supports between 500 supports;
B. HF gases are passed through into the process cavity, wherein the HF gases under the action of catalyzed gas with the technique The silicon dioxde reaction of intracavitary;And
C. it is passed through F into the process cavity2Gas or XeF2Gas, with the H in the process cavity2O reacts, the F2Gas Or XeF2The intake of gas is more than 1 with the ratio between the intake of HF gases in the step b:2.
2. silica release process as described in claim 1, which is characterized in that the step b and step c simultaneously into Row.
3. silica release process as described in claim 1, which is characterized in that the step c is laggard the step b's Row.
4. silica release process as claimed in claim 2 or claim 3, which is characterized in that after the step c, the dioxy SiClx release process further includes:
D. the O in the process cavity is detected2Content;And
If the O e1. detected2Content remains less than a default O within a predetermined period of time2Content then terminates the silica and releases Put technique.
5. silica release process as claimed in claim 4, which is characterized in that after the step d, the silica Release process further includes:
If the O e2. detected2Content does not remain less than the default O in the predetermined amount of time2Content then empties the work Then skill chamber repeats the step a~step d, until as the O detected2Content is kept in the predetermined amount of time Less than the default O2Above-mentioned steps e1 is executed when content.
6. silica release process as described in claim 1, which is characterized in that the catalyzed gas is gaseous water, second Alcohol, methanol or isopropanol.
7. silica release process as described in claim 1, which is characterized in that the HF gases are anhydrous HF gas.
8. silica release process as claimed in claim 4, which is characterized in that before the step a or described After step e1, which further includes:With nitrogen to being purged inside the process cavity.
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Citations (4)

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CN1567080A (en) * 2003-06-30 2005-01-19 元太科技工业股份有限公司 Structure releasing arrangement and method for preparing same
EP1531145A2 (en) * 2003-11-14 2005-05-18 Sony Corporation Etching method
CN102712462A (en) * 2009-09-25 2012-10-03 梅姆斯塔有限公司 Improved selectivity in a xenon difluoride etch process

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
WO2000046838A2 (en) * 1999-02-05 2000-08-10 Massachusetts Institute Of Technology Hf vapor phase wafer cleaning and oxide etching

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86105419A (en) * 1985-08-28 1987-04-29 Fsi公司 Gaseous process and equipment from the substrate removing films
CN1567080A (en) * 2003-06-30 2005-01-19 元太科技工业股份有限公司 Structure releasing arrangement and method for preparing same
EP1531145A2 (en) * 2003-11-14 2005-05-18 Sony Corporation Etching method
CN102712462A (en) * 2009-09-25 2012-10-03 梅姆斯塔有限公司 Improved selectivity in a xenon difluoride etch process

Non-Patent Citations (1)

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"用于悬浮纳米结构制作的氢氟酸气相刻蚀研究";张伟等;《半导体技术》;20091231;第34卷(第12期);摘要部分,正文"1 刻蚀机理"部分 *

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Address after: 201203 building 4, No. 1690, Cailun Road, free trade zone, Pudong New Area, Shanghai

Patentee after: Shengmei semiconductor equipment (Shanghai) Co., Ltd

Address before: 201203 Shanghai city Pudong New Area Zhangjiang High Tech Park of Shanghai Cailun Road No. fourth 1690

Patentee before: ACM (SHANGHAI) Inc.