JP5400528B2 - FINE PROCESSING AGENT AND FINE PROCESSING METHOD USING THE SAME - Google Patents
FINE PROCESSING AGENT AND FINE PROCESSING METHOD USING THE SAME Download PDFInfo
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- JP5400528B2 JP5400528B2 JP2009186741A JP2009186741A JP5400528B2 JP 5400528 B2 JP5400528 B2 JP 5400528B2 JP 2009186741 A JP2009186741 A JP 2009186741A JP 2009186741 A JP2009186741 A JP 2009186741A JP 5400528 B2 JP5400528 B2 JP 5400528B2
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- 238000003672 processing method Methods 0.000 title claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 74
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 74
- 239000003795 chemical substances by application Substances 0.000 claims description 61
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 50
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 50
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 15
- 239000005368 silicate glass Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 162
- 238000005530 etching Methods 0.000 description 60
- 239000000243 solution Substances 0.000 description 22
- 239000003990 capacitor Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000001039 wet etching Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000005380 borophosphosilicate glass Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 description 1
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000862969 Stella Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- -1 fatty acid ester Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ASVMCHUOIVTKQQ-UHFFFAOYSA-M triethyl(methyl)azanium;fluoride Chemical compound [F-].CC[N+](C)(CC)CC ASVMCHUOIVTKQQ-UHFFFAOYSA-M 0.000 description 1
Classifications
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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
- H01L21/31—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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Weting (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Liquid Crystal (AREA)
- Detergent Compositions (AREA)
- Paints Or Removers (AREA)
- ing And Chemical Polishing (AREA)
Description
本発明は、半導体装置、液晶表示装置、マイクロマシン（micro electro mechanical systems；MEMS）デバイス等の製造に於いて、エッチング処理や洗浄処理等に用いる微細加工処理剤及び微細加工処理方法に関し、より詳細には少なくともシリコン窒化膜、及びシリコン酸化膜が積層された構造物に対しエッチング処理や洗浄処理等に用いる微細加工処理剤及び微細加工処理方法に関する。 The present invention relates to a fine processing agent and a fine processing method used for etching processing, cleaning processing, and the like in the manufacture of semiconductor devices, liquid crystal display devices, micro electro mechanical systems (MEMS) devices, and the like. Relates to a fine processing agent and a fine processing method used for etching processing, cleaning processing, and the like for a structure in which at least a silicon nitride film and a silicon oxide film are stacked.
半導体素子の製造プロセスに於いて、ウエハ表面に成膜されたシリコン酸化膜、シリコン窒化膜、ポリシリコン膜、金属膜等を所望の形状にパターニングし、エッチングすることは最も重要なプロセスの一つである。そのエッチング技術の一種であるウェットエッチングに対しては、エッチング対象となる膜のみを選択的にエッチングすることが可能な微細加工処理方法が求められている。 One of the most important processes in the manufacturing process of semiconductor devices is to pattern and etch a silicon oxide film, silicon nitride film, polysilicon film, metal film, etc. formed on the wafer surface into a desired shape. It is. For wet etching, which is a kind of etching technique, a fine processing method capable of selectively etching only a film to be etched is required.
前記微細加工処理に於いてシリコン酸化膜をエッチング対象とするものとしては、例えば、バッファードフッ酸やフッ化水素酸を用いる方法が挙げられる。しかし、シリコン窒化膜とシリコン酸化膜が積層された積層膜に対し、前記バッファードフッ酸やフッ化水素酸を微細加工処理剤として用いると、シリコン窒化膜も同時にエッチングされる。その結果、所望の形状にパターニングすることが困難になる。 Examples of the method for etching a silicon oxide film in the fine processing include a method using buffered hydrofluoric acid or hydrofluoric acid. However, when the buffered hydrofluoric acid or hydrofluoric acid is used as the microfabrication processing agent for the laminated film in which the silicon nitride film and the silicon oxide film are laminated, the silicon nitride film is also etched at the same time. As a result, it becomes difficult to pattern into a desired shape.
この様な問題を解決し、シリコン酸化膜のみを選択的にエッチングすることが可能な微細加工処理方法としては、例えばフッ化水素酸にラウリル硫酸アンモニウム等の陰イオン性界面活性剤を添加したものを用いる方法が挙げられる（下記特許文献１参照）。しかし、前記微細加工処理剤では起泡性が極めて大きく、これにより半導体素子の製造プロセスに用いる微細加工処理方法としては適さない。 As a fine processing method that can solve such problems and selectively etch only the silicon oxide film, for example, a hydrofluoric acid added with an anionic surfactant such as ammonium lauryl sulfate The method of using is mentioned (refer the following patent document 1). However, the fine processing agent has a very high foaming property, which makes it unsuitable as a fine processing method used in a semiconductor element manufacturing process.
一方、微細加工処理剤を用いてウェットエッチングを行う半導体素子としては、例えばＤＲＡＭ（Dynamic Random Access Memory）が挙げられる。ＤＲＡＭセルはトランジスタ１個とキャパシタ１個で構成されたものである。このＤＲＡＭは過去３年で約４倍の高集積化が進められている。ＤＲＡＭの高集積化は、主にキャパシタの高集積化によるものである。よって、キャパシタの占有面積を縮小しながら、安定した記憶動作に必要な容量値を確保すべく、キャパシタ面積の増大、キャパシタ絶縁膜の薄膜化及び高誘電率膜の導入が行われている。 On the other hand, as a semiconductor element which performs wet etching using a fine processing agent, for example, a DRAM (Dynamic Random Access Memory) can be cited. The DRAM cell is composed of one transistor and one capacitor. This DRAM has been highly integrated about four times over the past three years. High integration of DRAM is mainly due to high integration of capacitors. Therefore, in order to secure a capacitance value necessary for stable storage operation while reducing the area occupied by the capacitor, the capacitor area is increased, the capacitor insulating film is thinned, and a high dielectric constant film is introduced.
前記キャパシタ絶縁膜としてはシリコン酸化膜が用いられており、これまではその薄膜化が検討されてきた。しかし、キャパシタの絶縁膜としてのシリコン酸化膜の薄膜化が、１ＭビットのＤＲＡＭで限界に達した。そのため、４ＭビットのＤＲＡＭでは、絶縁膜としてシリコン窒化膜が用いられている。更に高集積化が進むにつれてタンタル酸化膜の適用も開始されている。 As the capacitor insulating film, a silicon oxide film is used, and so far, its thinning has been studied. However, the thinning of the silicon oxide film as the capacitor insulating film has reached the limit with 1Mbit DRAM. Therefore, a silicon nitride film is used as an insulating film in a 4M bit DRAM. Furthermore, application of a tantalum oxide film has been started as higher integration progresses.
６４Ｍビット世代のＤＲＡＭのキャパシタ構造はシリンダ型である。シリンダ型のキャパシタ下部電極を形成した後、キャパシタ形成のため、成膜されたシリコン酸化膜をウェットエッチングによって除去する場合、従来のエッチング液を使用すると次に述べる問題が生じる。 The capacitor structure of a 64-Mbit generation DRAM is a cylinder type. When the silicon oxide film thus formed is removed by wet etching to form a capacitor after forming the cylinder-type capacitor lower electrode, the following problems occur when a conventional etching solution is used.
即ち、キャパシタ下部電極を形成した後に、成膜されたシリコン酸化膜をウェットエッチングにより除去する。更に、超純水によるリンスを行い、乾燥させる。この乾燥させる工程で、キャパシタ下部電極の間に存在する水の表面張力により、該下部電極が傾いて互いに付着する"リーニング（ｌｅａｎｉｎｇ）"現象が多発して、２−ビットフェイルを誘発するという問題がある。この為、下記特許文献２では、キャパシタ下部電極間にシリコン窒化膜からなる支持膜を形成する技術が開示されている。また、下記特許文献３には、ビットラインとの絶縁特性を向上させるためにシリコン窒化膜を絶縁膜として成膜する技術が開示され、更に、下記特許文献４には、シリコン窒化膜を後続のシリコン酸化膜のエッチング工程のエッチング停止膜として成膜する技術が開示されている。 That is, after the capacitor lower electrode is formed, the formed silicon oxide film is removed by wet etching. Further, rinse with ultrapure water and dry. In this drying process, the surface tension of water existing between the capacitor lower electrodes frequently causes a “leaning” phenomenon in which the lower electrodes are inclined and adhere to each other, thereby inducing 2-bit failure. There is. For this reason, Patent Document 2 below discloses a technique for forming a support film made of a silicon nitride film between capacitor lower electrodes. Patent Document 3 listed below discloses a technique for forming a silicon nitride film as an insulating film in order to improve the insulation characteristics with respect to the bit line. A technique for forming a film as an etching stop film in an etching process of a silicon oxide film is disclosed.
これらの半導体素子の製造プロセスに於いて従来のエッチング液を用いると、前記特許文献２に於ける支持膜としてのシリコン窒化膜や、特許文献３のシリコン窒化膜、特許文献４のエッチング停止膜としてのシリコン窒化膜がエッチング対象と共にエッチングされるという問題がある。 When a conventional etching solution is used in the manufacturing process of these semiconductor elements, the silicon nitride film as the support film in Patent Document 2, the silicon nitride film in Patent Document 3, and the etching stop film in Patent Document 4 are used. There is a problem that the silicon nitride film is etched together with the object to be etched.
本発明は前記問題点に鑑みなされたものであり、その目的は、少なくともシリコン酸化膜、及びシリコン窒化膜が積層された積層膜を微細加工する際に、シリコン酸化膜を選択的に微細加工することが可能な微細加工処理剤、及びそれを用いた微細加工処理方法を提供することにある。 The present invention has been made in view of the above-described problems, and an object of the present invention is to selectively finely process a silicon oxide film when finely processing a laminated film in which at least a silicon oxide film and a silicon nitride film are laminated. An object of the present invention is to provide a fine processing agent that can be used, and a fine processing method using the same.
本願発明者等は、前記従来の問題点を解決すべく、微細加工処理剤、及びそれを用いた微細加工処理方法について検討した。その結果、フッ化水素、又はフッ化アンモニウム若しくは第四級アンモニウムフロライドの少なくとも何れか一方を含む水溶液に、一定濃度の酸が添加された微細加工処理剤であると、シリコン酸化膜及びシリコン窒化膜が積層された積層膜に対し、シリコン酸化膜のみを選択的に微細加工できることを見出して、本発明を完成させるに至った。 The inventors of the present application have studied a fine processing agent and a fine processing method using the same in order to solve the conventional problems. As a result, when the microfabrication processing agent is obtained by adding a certain concentration of acid to an aqueous solution containing hydrogen fluoride or at least one of ammonium fluoride or quaternary ammonium fluoride, a silicon oxide film and silicon nitride The inventors have found that only a silicon oxide film can be selectively microfabricated with respect to a laminated film in which films are laminated, and have completed the present invention.
即ち、本発明に係る微細加工処理剤は、前記の課題を解決する為に、シリコン窒化膜及びシリコン酸化膜が形成された被処理物の微細加工に用いる微細加工処理剤であって、下記（Ａ）成分又は（Ｂ）成分の少なくとも何れか一方と、下記（Ｃ）成分と、下記（Ｄ）成分とを含み、下記（Ａ）成分又は（Ｂ）成分の少なくとも何れか一方と、（Ｃ）成分との含有量の合計が、微細加工処理剤の全体量に対し９０重量％以下である。
（Ａ）成分：０．０１重量％〜２０重量％のフッ化水素
（Ｂ）成分：０．１重量％〜２０重量％のフッ化アンモニウム、又は第四級アンモニウムフロライドの少なくとも何れか一方
（Ｃ）１重量％〜８０重量％の塩酸、硝酸、硫酸及びリン酸からなる群より選択される少なくとも何れか１種の酸
（Ｄ）水
That is, the microfabrication processing agent according to the present invention is a micromachining treatment agent used for microfabrication of an object on which a silicon nitride film and a silicon oxide film are formed in order to solve the above-described problems. A) at least one of component or (B), the following (C) component, and the following (D) component, at least one of the following (A) component or (B) component, and (C ) The total content of the components is 90% by weight or less based on the total amount of the fine processing agent.
(A) component: 0.01 wt% to 20 wt% hydrogen fluoride (B) component: at least one of 0.1 wt% to 20 wt% ammonium fluoride or quaternary ammonium fluoride C) 1 to 80% by weight of at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid (D) Water
前記構成によれば、前記（Ａ）成文又は（Ｂ）成文の少なくとも何れか一方と、前記（Ｃ）成文とを組み合わせた組成にすることにより、シリコン窒化膜に対するシリコン酸化膜のエッチングの選択比（シリコン酸化膜／シリコン窒化膜）を大きくすることができる。その結果、シリコン酸化膜及びシリコン窒化膜が順次積層された被処理物の微細加工に本発明の微細加工処理剤を適用すると、シリコン窒化膜に対してシリコン酸化膜の選択的な微細加工が可能になる。これにより、例えば、半導体素子の製造プロセスに於ける歩留まりの向上が図れる。 According to the above configuration, the etching selectivity of the silicon oxide film with respect to the silicon nitride film is obtained by combining at least one of the (A) composition and the (B) composition and the (C) composition. (Silicon oxide film / silicon nitride film) can be increased. As a result, when the micro-processing agent of the present invention is applied to the micro-processing of an object in which a silicon oxide film and a silicon nitride film are sequentially stacked, the silicon oxide film can be selectively micro-processed with respect to the silicon nitride film. become. Thereby, for example, the yield in the semiconductor element manufacturing process can be improved.
ここで、前記（Ｃ）成分の酸の含有量は１〜８０重量％の範囲内にする。下限値を１重量％にすることにより、酸の添加効果を発揮させることができ、シリコン酸化膜の選択的エッチングが可能になる。その一方、上限値を８０重量％にすることにより、シリコン酸化膜が微細加工されることで生成する反応生成物が、微細加工処理剤中に溶解するのを促し、当該シリコン酸化膜の微細加工を促進させることができる。また、微細加工処理剤の粘度の上昇も抑え、これにより超純水等のリンス剤による微細加工処理剤の除去性能を向上させることができる。尚、本発明に於ける「微細加工」とは、加工対象となる膜のエッチングや表面のクリーニングを含む意味である。 Here, the acid content of the component (C) is in the range of 1 to 80% by weight. By setting the lower limit to 1% by weight, the effect of acid addition can be exhibited, and the silicon oxide film can be selectively etched. On the other hand, by setting the upper limit to 80% by weight, the reaction product produced by finely processing the silicon oxide film is promoted to dissolve in the fine processing agent, and the silicon oxide film is finely processed. Can be promoted. In addition, an increase in the viscosity of the fine processing agent can be suppressed, thereby improving the removal performance of the fine processing agent with a rinse agent such as ultrapure water. In the present invention, “microfabrication” includes etching of a film to be processed and surface cleaning.
前記シリコン酸化膜は、自然酸化膜、熱シリコン酸化膜、ノンドープシリケートガラス膜、リンドープシリケートガラス膜、ボロンドープシリケートガラス膜、リンボロンドープシリケートガラス膜、ＴＥＯＳ膜又はフッ素含有シリコン酸化膜の何れかであることが好ましい。 The silicon oxide film is a natural oxide film, a thermal silicon oxide film, a non-doped silicate glass film, a phosphorus-doped silicate glass film, a boron-doped silicate glass film, a phosphorus-doped silicate glass film, a TEOS film, or a fluorine-containing silicon oxide film. It is preferable that
また、本発明に係る微細加工処理方法は、前記の課題を解決する為に、前記に記載の微細加工処理剤を用いて、シリコン酸化膜を選択的に微細加工するものである。 Moreover, in order to solve the above-mentioned problems, the microfabrication processing method according to the present invention selectively microfabricates a silicon oxide film using the microfabrication processing agent described above.
本発明は、前記に説明した手段により、以下に述べるような効果を奏する。
即ち、本発明によれば、シリコン酸化膜とシリコン窒化膜が少なくとも積層された積層膜に対し、シリコン酸化膜のみを選択的に微細加工処理することができるので、例えば半導体装置、液晶表示装置、マイクロマシンデバイス等の製造に於いて好適な微細加工を可能にする。
The present invention has the following effects by the means described above.
That is, according to the present invention, only the silicon oxide film can be selectively finely processed with respect to the laminated film in which at least the silicon oxide film and the silicon nitride film are laminated. For example, a semiconductor device, a liquid crystal display device, It enables fine processing suitable for manufacturing micromachine devices and the like.
本発明の実施の一形態について、以下に説明する。
本実施の形態に係る微細加工処理剤は、下記（Ａ）成分又は（Ｂ）成分の少なくとも何れか一方と、下記（Ｃ）成分と、下記（Ｄ）成分とを含む。
（Ａ）成分：０．０１重量％〜２０重量％のフッ化水素
（Ｂ）成分：０．１重量％〜２０重量％のフッ化アンモニウム、又は第四級アンモニウムフロライドの少なくとも何れか一方
（Ｃ）１重量％〜８０重量％の塩酸、硝酸、硫酸及びリン酸からなる群より選択される少なくとも何れか１種の酸
（Ｄ）水
One embodiment of the present invention will be described below.
The fine processing agent according to the present embodiment includes at least one of the following component (A) or component (B), the following component (C), and the following component (D).
(A) component: 0.01 wt% to 20 wt% hydrogen fluoride (B) component: at least one of 0.1 wt% to 20 wt% ammonium fluoride or quaternary ammonium fluoride C) 1 to 80% by weight of at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid (D) Water
前記（Ａ）成分であるフッ化水素の含有量は、微細加工処理剤の全体量に対し０．０１〜２０重量％の範囲内であり、０．１〜１０重量％の範囲内であることが好適である。フッ化水素の含有量が０．０１重量％未満であると、フッ化水素の濃度制御が困難になる為、シリコン酸化膜に対するエッチレートのバラツキが大きくなる場合がある。また、フッ化水素の含有量が２０重量％を超えると、シリコン酸化膜に対するエッチレートが大きくなり過ぎ、エッチングの制御性が低下する。また、フッ化水素ガスの蒸発が顕著になり、微細加工処理剤の取り扱いが困難になる場合がある。 The content of hydrogen fluoride as the component (A) is in the range of 0.01 to 20% by weight and in the range of 0.1 to 10% by weight with respect to the total amount of the fine processing agent. Is preferred. When the content of hydrogen fluoride is less than 0.01% by weight, it is difficult to control the concentration of hydrogen fluoride, and thus there may be a large variation in the etch rate with respect to the silicon oxide film. On the other hand, if the content of hydrogen fluoride exceeds 20% by weight, the etching rate for the silicon oxide film becomes too high, and the controllability of etching is lowered. Further, the evaporation of hydrogen fluoride gas becomes remarkable, and it may be difficult to handle the fine processing agent.
前記（Ｂ）成分としては、フッ化アンモニウム又は第四級アンモニウムフロライドの少なくとも何れか一方を含んでいればよい。前記第四級アンモニウムフロライドとしては特に限定されず、例えば、テトラメチルアンモニウムフロライド、テトラエチルアンモニウムフロライド、トリエチルメチルアンモニウムフロライド、コリンフロライドなどが挙げられる。 The component (B) only needs to contain at least one of ammonium fluoride and quaternary ammonium fluoride. The quaternary ammonium fluoride is not particularly limited, and examples thereof include tetramethylammonium fluoride, tetraethylammonium fluoride, triethylmethylammonium fluoride, and choline fluoride.
前記（Ｂ）成分の含有量は、微細加工処理剤の全体量に対し０．１〜２０重量％の範囲内であり、０．５〜１０重量％の範囲内であることが好適である。（Ｂ）成分の含有量が０．１重量％未満であると、微細加工処理剤における（Ｂ）成分の濃度制御が困難になり、シリコン酸化膜に対するエッチレートのバラツキが大きくなる場合がある。また、（Ｂ）成分の含有量が２０重量％を超えると、（Ｂ）成分の飽和溶解度に近づくため、微細加工処理剤の液温によっては結晶が析出する恐れがある。 The content of the component (B) is in the range of 0.1 to 20% by weight and preferably in the range of 0.5 to 10% by weight with respect to the total amount of the fine processing agent. When the content of the component (B) is less than 0.1% by weight, it is difficult to control the concentration of the component (B) in the fine processing agent, and the variation in the etch rate with respect to the silicon oxide film may increase. Further, when the content of the component (B) exceeds 20% by weight, the saturation solubility of the component (B) is approached, so that crystals may precipitate depending on the liquid temperature of the fine processing agent.
前記（Ｃ）成分は塩酸、硝酸、硫酸、及びリン酸からなる群より選択される少なくとも何れか１種の酸である。これらの酸のうち、シリコン窒化膜に対するシリコン酸化膜の選択性の観点からは硫酸が好ましい。 The component (C) is at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Of these acids, sulfuric acid is preferred from the viewpoint of the selectivity of the silicon oxide film relative to the silicon nitride film.
前記（Ｃ）成分の含有量は、微細加工処理剤の全体量に対し１〜８０重量％の範囲内であり、４０〜７０重量％の範囲内であることが好適である。（Ｃ）成分の含有量が１重量％未満であると、酸の添加効果を発揮させることができず、シリコン酸化膜の選択的なエッチング等が困難になる場合がある。また、（Ｃ）成分の含有量が８０重量％を超えると、シリコン酸化膜のエッチングで生成した反応生成物の微細加工処理剤中への溶解が抑制され、シリコン酸化膜のエッチングが阻害される場合がある。また、微細加工処理剤の粘度が大きくなり、超純水等のリンス剤による微細加工処理剤のリンス除去性能が低減する場合もある。 The content of the component (C) is in the range of 1 to 80% by weight and preferably in the range of 40 to 70% by weight with respect to the total amount of the fine processing agent. If the content of the component (C) is less than 1% by weight, the effect of adding an acid cannot be exhibited, and selective etching of the silicon oxide film may be difficult. On the other hand, when the content of the component (C) exceeds 80% by weight, dissolution of the reaction product generated by etching the silicon oxide film into the fine processing agent is suppressed, and etching of the silicon oxide film is inhibited. There is a case. In addition, the viscosity of the fine processing agent may increase, and the rinse removal performance of the fine processing agent with a rinse agent such as ultrapure water may decrease.
前記（Ａ）成分又は（Ｂ）成分の少なくとも何れか一方と、（Ｃ）成分との含有量の合計は、微細加工処理剤の全体量に対して９０重量％以下であり、７０重量％以下であることが好適である。（Ａ）成分又は（Ｂ）成分の少なくとも何れか一方と、（Ｃ）成分との合計含有量を９０重量％以下にすることで、シリコン酸化膜がエッチングされた際に生じる反応生成物が微細加工処理剤中に溶解するのを促し、シリコン酸化膜に対するエッチレートのバラツキが抑制することができる。また、微細加工処理剤の粘度の上昇も抑え、これにより超純水等のリンス剤による微細加工処理剤の除去性能を向上させることができる。 The total content of at least one of the component (A) or the component (B) and the component (C) is 90% by weight or less and 70% by weight or less based on the total amount of the fine processing agent. It is preferable that By making the total content of at least one of the component (A) or the component (B) and the component (C) 90% by weight or less, the reaction product generated when the silicon oxide film is etched is fine. It is possible to promote dissolution in the processing agent and suppress variation in the etch rate with respect to the silicon oxide film. In addition, an increase in the viscosity of the fine processing agent can be suppressed, thereby improving the removal performance of the fine processing agent with a rinse agent such as ultrapure water.
本実施の形態に係る微細加工処理剤には、第３成分が含有されていてもよい。第３成分としては、例えば、界面活性剤が挙げられる。前記界面活性剤としては特に限定されないが、例えば、微細加工処理剤のｐＨが２より小さい場合は、ポリエチレングリコールアルキルエーテル、ポリエチレングリコールアルキルフェニルエーテル、ポリエチレングリコール脂肪酸エステル等の非イオン界面活性剤が好適である。また、微細加工処理剤のｐＨが２以上の場合は、脂肪族アルコール、脂肪族カルボン酸、ハイドロフルオロアルキルアルコール、ハイドロフルオロアルキルカルボン酸、ハイドロフルオロアルキルカルボン酸塩、脂肪族アミン塩、及び脂肪族スルホン酸からなる群より選択される少なくとも何れか１種が好適である。更に、微細加工処理剤のｐＨが２以上の場合、微細加工処理剤は固体でもよく、液体でもよい。 The fine processing agent according to the present embodiment may contain a third component. Examples of the third component include a surfactant. The surfactant is not particularly limited. For example, when the pH of the fine processing agent is less than 2, nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, and polyethylene glycol fatty acid ester are preferable. It is. Moreover, when the pH of the fine processing agent is 2 or more, aliphatic alcohol, aliphatic carboxylic acid, hydrofluoroalkyl alcohol, hydrofluoroalkyl carboxylic acid, hydrofluoroalkyl carboxylate, aliphatic amine salt, and aliphatic At least one selected from the group consisting of sulfonic acids is preferred. Furthermore, when the pH of the fine processing agent is 2 or more, the fine processing agent may be solid or liquid.
前記界面活性剤の添加量は、０．００１〜０．１重量％の範囲内であることが好適であり、０．００３〜０．０５重量％の範囲内であることがより好適である。界面活性剤を添加することにより、エッチング処理を施したシリコン窒化膜や半導体基板等の表面の荒れを抑制することができる。更に、従来の微細加工処理剤であると、超高集積化に伴い微細パターンが施された半導体基板表面に局部的に残留しやすく、レジスト間隔が０．５μｍ程度あるいはそれ以下になると均一的にエッチングすることがより困難である。しかし、界面活性剤を添加した本発明の微細加工処理剤をエッチング液として使用した場合、半導体基板表面への濡れ性が改善され、エッチングの基板面内に於ける均一性が改善される。但し、前記添加量が０．００１重量％未満であると、微細加工処理剤の表面張力が十分に低下しない為に、濡れ性の向上効果が不十分になる場合がある。また、前記添加量が０．１重量％を超えると、それに見合う効果が得られないだけでなく、消泡性が悪化してエッチング面に泡が付着し、エッチングむらが生じたり、微細間隙に泡が入り込んでエッチング不良を生じる場合がある。 The addition amount of the surfactant is preferably in the range of 0.001 to 0.1% by weight, and more preferably in the range of 0.003 to 0.05% by weight. By adding the surfactant, it is possible to suppress the roughness of the surface of the silicon nitride film or semiconductor substrate subjected to the etching process. Furthermore, conventional fine processing agents tend to remain locally on the surface of a semiconductor substrate on which a fine pattern has been applied due to ultra-high integration, and uniformly when the resist interval is about 0.5 μm or less. It is more difficult to etch. However, when the fine processing agent of the present invention to which a surfactant is added is used as an etching solution, the wettability to the surface of the semiconductor substrate is improved, and the uniformity of etching in the substrate surface is improved. However, if the addition amount is less than 0.001% by weight, the surface tension of the fine processing agent is not sufficiently lowered, and the effect of improving wettability may be insufficient. Further, if the addition amount exceeds 0.1% by weight, not only the effect corresponding to that can not be obtained, but also the defoaming property deteriorates, the bubbles adhere to the etched surface, the etching unevenness occurs, or the fine gaps are formed. Bubbles may enter and cause etching failure.
本実施の形態の微細加工処理剤は、その効果を阻害しない範囲内に於いて、界面活性剤以外の添加剤を混合することも可能である。前記添加剤としては、例えば、過酸化水素、キレート剤等が例示できる。 In the fine processing agent of the present embodiment, additives other than the surfactant can be mixed within a range that does not impair the effect. Examples of the additive include hydrogen peroxide and a chelating agent.
本実施の形態に係る微細加工処理剤は、各（Ａ）成分〜（Ｄ）成分を任意の順序で混合することにより製造することができる。尚、（Ｂ）成分は、その原料が水酸化物である場合は適宜フッ酸を加えて中和し、フッ化物とすることにより得られる。また、水酸化物である原料をフッ酸により中和させることなく、（Ａ）成分であるフッ化水素を少なくとも含む溶液に加えることにより、当該フッ化水素の一部と中和反応をさせ、結果的に溶液中に（Ｂ）成分が含んだ態様としてもよい。ここで、（Ｂ）成分の原料が水酸化物である場合、その様な水酸化物としては、例えば、水酸化アンモニウム、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化トリエチルメチルアンモニウム、又はコリン等のアンモニウムの水酸化物が挙げられる。 The fine processing agent according to the present embodiment can be produced by mixing the components (A) to (D) in any order. In addition, (B) component is obtained by adding a hydrofluoric acid suitably and neutralizing it, when the raw material is a hydroxide, and making it into a fluoride. Further, without neutralizing the raw material which is a hydroxide with hydrofluoric acid, by adding to a solution containing at least hydrogen fluoride which is the component (A), a neutralization reaction with a part of the hydrogen fluoride is performed, As a result, it is good also as an aspect which (B) component contained in the solution. Here, when the raw material of the component (B) is a hydroxide, examples of such a hydroxide include ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylmethylammonium hydroxide, or Examples thereof include ammonium hydroxides such as choline.
次に、本実施の形態に係る微細加工処理剤を用いた微細加工処理方法について、ウェットエッチングを例にして説明する。 Next, a microfabrication processing method using the microfabrication processing agent according to the present embodiment will be described using wet etching as an example.
本実施の形態に係る微細加工処理剤は、例えば、基板上にシリコン窒化膜及びシリコン酸化膜が形成された被処理物に対して使用される。具体的には、基板上にシリコン窒化膜及びシリコン酸化膜同一面内に設けられたものや、シリコン窒化膜及びシリコン酸化膜が順次積層された積層膜、あるいはシリコン酸化膜及びシリコン窒化膜が順次積層された積層膜が挙げられる。前記シリコン酸化膜としては、自然酸化膜、熱シリコン酸化膜、ノンドープシリケートガラス膜、リンドープシリケートガラス膜、ボロンドープシリケートガラス膜、リンボロンドープシリケートガラス膜、ＴＥＯＳ膜、フッ素含有シリコン酸化膜等が挙げられる。 The microfabrication processing agent according to the present embodiment is used for an object to be processed in which a silicon nitride film and a silicon oxide film are formed on a substrate, for example. Specifically, a silicon nitride film and a silicon oxide film provided on the same plane on the substrate, a stacked film in which a silicon nitride film and a silicon oxide film are sequentially stacked, or a silicon oxide film and a silicon nitride film are sequentially stacked. The laminated film laminated | stacked is mentioned. Examples of the silicon oxide film include a natural oxide film, a thermal silicon oxide film, a non-doped silicate glass film, a phosphorus-doped silicate glass film, a boron-doped silicate glass film, a phosphorus-doped silicate glass film, a TEOS film, and a fluorine-containing silicon oxide film. Can be mentioned.
本実施の形態に係る微細加工処理剤は、種々のウェットエッチング法に採用される。エッチング方法としては、浸漬式やスプレー式等があるが、いずれの方法にも本発明の微細加工処理剤は採用され得る。浸漬式は、エッチング工程での蒸発により微細加工処理剤の組成変化が少ないので好適である。 The fine processing agent according to the present embodiment is employed in various wet etching methods. As an etching method, there are an immersion method, a spray method, and the like, and the microfabrication processing agent of the present invention can be adopted in any method. The immersion method is preferable because the composition change of the fine processing agent is small due to evaporation in the etching process.
微細加工処理剤をエッチング液として使用した場合のエッチング温度（微細加工処理剤の液温）は、５〜５０℃の範囲内であることが好適であり、１５〜３５℃の範囲内であることがより好適であり、２０〜３０℃の範囲内であることが更に好適である。前記範囲内であると、微細加工処理剤の蒸発を抑制することができ、組成変化を防止することができる。また、高温度では微細加工処理剤の蒸発によりエッチレートの制御が困難になり、低温度では微細加工処理剤中の成分が結晶化しやすくなり、エッチレートの低下、液中粒子の増加するというデメリットを回避できる。尚、エッチング温度によっては膜毎にエッチレートが変化するので、シリコン酸化膜に対するエッチレートとシリコン窒化膜に対するエッチレートとの差も影響を受ける場合がある。 When the fine processing agent is used as an etching solution, the etching temperature (the liquid temperature of the fine processing agent) is preferably in the range of 5 to 50 ° C, and in the range of 15 to 35 ° C. Is more preferable, and it is still more preferable that it exists in the range of 20-30 degreeC. Within the above range, evaporation of the fine processing agent can be suppressed, and a change in composition can be prevented. In addition, it is difficult to control the etching rate due to evaporation of the fine processing agent at high temperatures, and the disadvantage is that the components in the micro processing agent are likely to crystallize at low temperatures, resulting in a decrease in etch rate and an increase in liquid particles. Can be avoided. Note that since the etch rate varies from film to film depending on the etching temperature, the difference between the etch rate for the silicon oxide film and the etch rate for the silicon nitride film may be affected.
また、本実施の形態の微細加工処理剤に於いては、２５℃に於けるシリコン酸化膜に対するエッチレートが１〜１００００ｎｍ／分の範囲内であることが好適であり、１５〜３０００ｎｍ／分の範囲内であることがより好適である。エッチレートが１ｎｍ／分未満であると、エッチング等の微細加工処理に時間を要し、生産効率の低下を招来する場合がある。また、１００００ｎｍ／分を超えると、エッチング後の膜厚の制御性の低下や基板表面（シリコン酸化膜等の形成面とは反対側の面）の荒れが顕著になり、歩留まりが低下する場合がある。 In the fine processing agent of the present embodiment, the etch rate for the silicon oxide film at 25 ° C. is preferably in the range of 1 to 10,000 nm / min, and 15 to 3000 nm / min. More preferably within the range. If the etch rate is less than 1 nm / min, it takes time for fine processing such as etching, which may lead to a decrease in production efficiency. Further, if it exceeds 10,000 nm / min, the controllability of the film thickness after etching and the roughness of the substrate surface (surface opposite to the surface on which the silicon oxide film etc. are formed) become prominent and the yield may decrease. is there.
以下に、この発明の好適な実施例を例示的に詳しく説明する。但し、この実施例に記載されている材料や配合量等は、特に限定的な記載がない限りは、この発明の範囲をそれらのみに限定する趣旨のものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the present invention only to those unless otherwise specified.
（シリコン酸化膜及びシリコン窒化膜に対するエッチレート）
光学式膜厚測定装置（ナノメトリクスジャパン（株）社製、Ｎａｎｏｓｐｅｃ６１００）を用いてエッチング前後のシリコン酸化膜、及びシリコン窒化膜の膜厚を測定し、エッチングによる膜厚の変化を測定した。３つの異なるエッチング時間に於いて前記測定を繰り返し実施し、エッチレートを算出した。尚、被処理物としては、シリコン窒化膜、又はシリコン酸化膜がそれぞれ基板上に形成されたものを用いた。
(Etch rate for silicon oxide film and silicon nitride film)
The film thickness of the silicon oxide film and the silicon nitride film before and after etching was measured using an optical film thickness measuring device (Nanospec 6100, manufactured by Nanometrics Japan Co., Ltd.), and the change in film thickness due to etching was measured. The above measurement was repeated at three different etching times to calculate the etch rate. As the object to be processed, a silicon nitride film or a silicon oxide film formed on the substrate was used.
（実施例１）
フッ化水素（ステラケミファ（株）製、半導体用高純度グレード、濃度５０重量％）１０重量部と、超純水７重量部とを混合した溶液に、（Ｃ）成分としての硫酸（三菱化学（株）製、濃度９６重量％）８３重量部を添加し、攪拌混合した後、混合液を２５℃に調温し３時間静置した。これにより、フッ化水素５重量％、硫酸８０重量％のエッチング液（微細加工処理剤）を調製した。
Example 1
In a solution obtained by mixing 10 parts by weight of hydrogen fluoride (manufactured by Stella Chemifa Co., Ltd., high purity grade for semiconductor, concentration 50% by weight) and 7 parts by weight of ultrapure water, sulfuric acid (Mitsubishi Chemical After 83 parts by weight were added and stirred and mixed, the mixture was adjusted to 25 ° C. and allowed to stand for 3 hours. Thus, an etching solution (fine processing agent) of 5 wt% hydrogen fluoride and 80 wt% sulfuric acid was prepared.
次に、前記シリコン窒化膜、又はシリコン酸化膜が形成されたそれぞれの基板を浸漬させ、シリコン酸化膜としてのＢＰＳＧ膜、及びシリコン窒化膜に対するエッチレートを測定した。更に、エッチレートの選択比（シリコン酸化膜／シリコン窒化膜）を評価した。尚、このときのエッチング液の液温は２５℃とした。結果を下記表１に示す。 Next, the respective substrates on which the silicon nitride film or the silicon oxide film was formed were immersed, and the etch rates for the BPSG film as the silicon oxide film and the silicon nitride film were measured. Furthermore, the etch rate selectivity (silicon oxide film / silicon nitride film) was evaluated. In addition, the liquid temperature of the etching liquid at this time was 25 degreeC. The results are shown in Table 1 below.
（実施例２〜９）
実施例２〜９に於いては、表１に示す通りに、（Ａ）成分（フッ化水素）の含有量と、（Ｂ）成分の含有量及び種類と、（Ｃ）成分の含有量及び種類とを変更したこと以外は、前記実施例１と同様にしてエッチング液を調製した。更に、各実施例で得られたエッチング液を用いて、ＢＰＳＧ膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比（シリコン酸化膜／シリコン窒化膜）を評価した。結果を下記表１に示す。
(Examples 2-9)
In Examples 2 to 9, as shown in Table 1, the content of component (A) (hydrogen fluoride), the content and type of component (B), the content of component (C) and An etching solution was prepared in the same manner as in Example 1 except that the type was changed. Furthermore, using the etching solution obtained in each example, the etching rate with respect to the BPSG film and the silicon nitride film and the selectivity of the etching rate (silicon oxide film / silicon nitride film) were evaluated. The results are shown in Table 1 below.
（比較例１、２）
比較例１に於いては、表１に示す通りに（Ｃ）成分の酸を添加しなかったこと以外は、前記実施例１と同様にしてエッチング液を調製した。また、比較例２に於いては、表１に示す通りに（Ｃ）成分の酸を添加しなかったこと以外は、前記実施例７と同様にしてエッチング液を調製した。更に、各比較例で得られたエッチング液を用いて、実施例１と同様にして、ＢＰＳＧ膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比（シリコン酸化膜／シリコン窒化膜）を評価した。結果を下記表１に示す。
(Comparative Examples 1 and 2)
In Comparative Example 1, an etching solution was prepared in the same manner as in Example 1 except that the acid of component (C) was not added as shown in Table 1. In Comparative Example 2, an etching solution was prepared in the same manner as in Example 7 except that the acid of component (C) was not added as shown in Table 1. Further, using the etching solutions obtained in the comparative examples, the etching rate with respect to the BPSG film and the silicon nitride film and the selectivity of the etching rate (silicon oxide film / silicon nitride film) were evaluated in the same manner as in Example 1. . The results are shown in Table 1 below.
（結果）
下記表１からも明らかな通り、（Ｃ）成分である酸が添加されていない比較例１及び２に係るエッチング液では、ＢＰＳＧ膜の選択的なエッチングが抑制されており、シリコン窒化膜に対するシリコン酸化膜のエッチレートの選択比（シリコン酸化膜／シリコン窒化膜）を大きくすることはできなかった。
(result)
As apparent from Table 1 below, in the etching solutions according to Comparative Examples 1 and 2 to which no acid (C) is added, selective etching of the BPSG film is suppressed, and silicon with respect to the silicon nitride film is suppressed. The selectivity of the oxide film etch rate (silicon oxide film / silicon nitride film) could not be increased.
一方、実施例１〜９に係るエッチング液の様に、（Ａ）成分又は（Ｂ）成分の少なくとも何れか一方と、（Ｃ）成分とを含む組成であると、シリコン酸化膜に対するエッチレートを選択的に大きくすることができ、シリコン窒化膜に対するシリコン酸化膜のエッチレートの選択比（シリコン酸化膜／シリコン窒化膜）が大きくできることが確認された。 On the other hand, when the composition includes at least one of the component (A) or the component (B) and the component (C) as in the etching solutions according to Examples 1 to 9, the etch rate for the silicon oxide film is increased. It was confirmed that the etching rate of the silicon oxide film with respect to the silicon nitride film can be increased selectively (silicon oxide film / silicon nitride film).
（実施例１０〜１４）
実施例１０〜１４に於いては、表２に示す通りに、（Ａ）成分（フッ化水素）の含有量と、（Ｂ）成分の含有量及び種類と、（Ｃ）成分の含有量及び種類とを変更したこと以外は、前記実施例１と同様にしてエッチング液を調製した。更に、各実施例で得られたエッチング液を用いて、実施例１と同様にして、シリコン酸化膜としてのノンドープシリケートガラス膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比（シリコン酸化膜／シリコン窒化膜）を評価した。結果を下記表２に示す。
(Examples 10 to 14)
In Examples 10 to 14, as shown in Table 2, the content of component (A) (hydrogen fluoride), the content and type of component (B), the content of component (C) and An etching solution was prepared in the same manner as in Example 1 except that the type was changed. Further, using the etching solution obtained in each example, in the same manner as in Example 1, the etch rate with respect to the non-doped silicate glass film and the silicon nitride film as the silicon oxide film, and the selectivity of the etch rate (silicon oxide film / (Silicon nitride film) was evaluated. The results are shown in Table 2 below.
（比較例３、４）
比較例３に於いては、表２に示す通りに（Ｃ）成分を添加しなかったこと以外は、前記実施例１０と同様にしてエッチング液を調製した。また、比較例４に於いては、表２に示す通りに（Ｂ）成分を添加しなかったこと以外は、前記実施例１１と同様にしてエッチング液を調製した。更に、各比較例で得られたエッチング液を用いて、実施例１と同様にして、ノンドープシリケートガラス膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比（シリコン酸化膜／シリコン窒化膜）を評価した。結果を下記表２に示す。
(Comparative Examples 3 and 4)
In Comparative Example 3, an etching solution was prepared in the same manner as in Example 10 except that the component (C) was not added as shown in Table 2. In Comparative Example 4, an etching solution was prepared in the same manner as in Example 11 except that the component (B) was not added as shown in Table 2. Further, using the etching solution obtained in each comparative example, the etching rate for the non-doped silicate glass film and the silicon nitride film and the selectivity of the etching rate (silicon oxide film / silicon nitride film) were set in the same manner as in Example 1. evaluated. The results are shown in Table 2 below.
（結果）
下記表２からも明らかな通り、（Ｃ）成分である酸が添加されていない比較例３及び４に係るエッチング液では、ノンドープシリケートガラス膜の選択的なエッチングが抑制されており、シリコン窒化膜に対するシリコン酸化膜のエッチレートの選択比（シリコン酸化膜／シリコン窒化膜）を大きくすることはできなかった。
(result)
As apparent from Table 2 below, in the etching solutions according to Comparative Examples 3 and 4 to which no acid as the component (C) was added, selective etching of the non-doped silicate glass film was suppressed, and the silicon nitride film It was not possible to increase the etching ratio (silicon oxide film / silicon nitride film) of the silicon oxide film to the silicon oxide film.
一方、実施例１０〜１４に係るエッチング液の様に、（Ａ）成分又は（Ｂ）成分の少なくとも何れか一方と、（Ｃ）成分とを含む組成であると、シリコン酸化膜に対するエッチレートを選択的に大きくすることができ、シリコン窒化膜に対するシリコン酸化膜のエッチレートの選択比（シリコン酸化膜／シリコン窒化膜）が大きくできることが確認された。 On the other hand, when the composition includes at least one of the component (A) or the component (B) and the component (C) like the etching solutions according to the examples 10 to 14, the etch rate for the silicon oxide film is increased. It was confirmed that the etching rate of the silicon oxide film with respect to the silicon nitride film can be increased selectively (silicon oxide film / silicon nitride film).
Claims (3)
前記微細加工処理剤は、シリコン窒化膜に対してシリコン酸化膜を選択的に微細加工することができ、
下記（Ａ）成分と、下記（Ｂ）成分と、下記（Ｃ）成分と、下記（Ｄ）成分とを含み、
下記（Ａ）成分と、下記（Ｂ）成分と、下記（Ｃ）成分との含有量の合計が、微細加工処理剤の全体量に対し９０重量％以下である微細加工処理剤。
（Ａ）成分：０．０１重量％〜２０重量％のフッ化水素
（Ｂ）成分：０．１重量％〜２０重量％のフッ化アンモニウム、又は第四級アンモニウムフロライドの少なくとも何れか一方
（Ｃ）成分：１重量％〜８０重量％の塩酸、硝酸、硫酸及びリン酸からなる群より選択される少なくとも何れか１種の酸
（Ｄ）成分：水 A microfabrication processing agent used for microfabrication of an object to be processed on which a silicon nitride film and a silicon oxide film are formed,
The fine processing agent can selectively finely process the silicon oxide film with respect to the silicon nitride film,
Includes a following component (A), min formed the following (B), and the following component (C), and the following component (D),
And the following component (A), min formed the following (B), the total content of the following component (C), the fine processing agent is 90 wt% or less relative to the total amount of the fine processing agent.
(A) component: 0.01 wt% to 20 wt% hydrogen fluoride (B) component: at least one of 0.1 wt% to 20 wt% ammonium fluoride or quaternary ammonium fluoride Component C) 1% to 80% by weight of at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid (D) Component: water
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