KR20120002426A - Method of preventing oxidation of metal film surface and solution of preventing oxidation - Google Patents
Method of preventing oxidation of metal film surface and solution of preventing oxidation Download PDFInfo
- Publication number
- KR20120002426A KR20120002426A KR1020110051163A KR20110051163A KR20120002426A KR 20120002426 A KR20120002426 A KR 20120002426A KR 1020110051163 A KR1020110051163 A KR 1020110051163A KR 20110051163 A KR20110051163 A KR 20110051163A KR 20120002426 A KR20120002426 A KR 20120002426A
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- compound
- antioxidant
- metal film
- film
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 239000004065 semiconductor Substances 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 97
- 239000003963 antioxidant agent Substances 0.000 claims description 91
- 239000007788 liquid Substances 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 37
- -1 phosphorus compound Chemical class 0.000 claims description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 150000007514 bases Chemical class 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003242 anti bacterial agent Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000004380 ashing Methods 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004599 antimicrobial Substances 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003064 anti-oxidating effect Effects 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- 229960004889 salicylic acid Drugs 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
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- 239000004310 lactic acid Substances 0.000 claims description 5
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- 230000002265 prevention Effects 0.000 claims description 5
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical group C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 claims description 3
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- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011229 interlayer Substances 0.000 abstract description 11
- 230000004888 barrier function Effects 0.000 abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 239000010937 tungsten Substances 0.000 abstract description 3
- 235000006708 antioxidants Nutrition 0.000 description 79
- 239000000243 solution Substances 0.000 description 38
- 230000007797 corrosion Effects 0.000 description 25
- 238000005260 corrosion Methods 0.000 description 25
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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
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
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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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28568—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table the conductive layers comprising transition metals
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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
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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- Power Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Dicing (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
본 발명은 반도체 소자의 제조 과정에 적용되는 금속막 표면의 산화방지방법 및 산화방지액에 관한 것이다.The present invention relates to an anti-oxidation method and an antioxidant solution on the surface of a metal film applied in the manufacturing process of a semiconductor device.
반도체 소자의 제조에 있어서의 다이싱(dicing) 공정에는 웨이퍼 상에 형성된 집적회로(반도체 기판)를 각각의 소자 사이즈로 구분되도록 절단 가공이 실시된다. 이 절단 가공에는 다이아몬드제의 원형 회전 칼날 등의 다이싱 블레이드가 적용되고 이것을 고속회전시켜 웨이퍼 상의 집적회로를 정밀하게 분할해 간다. 이 때 발생되는 열의 냉각과 그 절단에 따라 발생되는 절삭 조각을 씻어내는 것을 목적으로 반도체 웨이퍼 상에 다량의 순수가 공급된다.In a dicing step in the manufacture of a semiconductor element, a cutting process is performed to divide the integrated circuit (semiconductor substrate) formed on the wafer into respective element sizes. In this cutting process, a dicing blade such as a circular rotary blade made of diamond is applied, which is rotated at a high speed to precisely divide the integrated circuit on the wafer. A large amount of pure water is supplied onto the semiconductor wafer for the purpose of cooling the heat generated at this time and washing off the cutting chips generated by the cutting.
다이싱 가공이 행해질 때의 반도체 기판은 통상, 금속막 표면이 노출된 부분을 갖는다. 예컨대, 도 2에 나타낸 것에는 패드(5')를 구성하는 알루미늄-구리 합금막(52')의 표면이 개구부(H)에 의해 노출된 상태로 되어 있다. 그리고, 이 다이싱 공정 후에 분할된 반도체 기판은 회로기판 등에 설치되고 이 패드를 통하여 본딩 와이어 등에 의해 전기적으로 접속된다. 그 때문에, 그 금속표면은 청정하여 양호한 도전성이 확보되는 상태인 것이 요구된다.The semiconductor substrate at the time of a dicing process has a part which the metal film surface was exposed normally. For example, in FIG. 2, the surface of the aluminum-copper alloy film 52 'which comprises the pad 5' is exposed by the opening part H. As shown in FIG. The semiconductor substrate divided after this dicing step is provided on a circuit board or the like and electrically connected to each other by a bonding wire or the like through this pad. Therefore, the metal surface is required to be in a clean state and to ensure good conductivity.
그런데, 상기 다이싱 공정을 행할 때에 다량의 순수가 공급되기 때문에, 반도체 기판의 금속막 표면도 이 순수에 노출되어 그 영향을 받는 경우가 있다. 예컨대, 금속막으로 구성한 패드에 있어서, 그 표면이 산화되어 알루미늄이나 구리 등을 금속막 재료로서 사용했을 때에 피팅 부식(pitting corrosion)이라고 불리는 부식(침식)(c)이 진행되는 경우가 있다(도 2 참조). 그 결과, 도통 불량에 의한 수율의 저하가 발생한다. 상술한 바와 같은 부식을 최대한 저감 또는 방지하고 싶다. 또한, 최근 패드의 구성 재료로서 알루미늄-구리 합금이 주류가 되어 왔다. 발명자의 확인에 의하면, 이 알루미늄-구리 합금을 금속막으로서 사용했을 때에 상술한 바와 같은 부식의 진행이 현저해지는 경향이 있는 것을 알 수 있었다. 여기서, 예컨대, 반도체 기판의 금속막 표면에 대하여 일본특허공개 2009-531512호 공보나 일본특허공개 2003-55254호 공보에 개시된 산화방지액을 사용하여 금속막 표면의 산화에 의한 부식(침식)을 억제 또는 방지하는 것도 가능하지만, 이러한 산화에 의한 부식을 더욱 억제하거나 방지하는 것이 항상 요구되고 있다.By the way, since a large amount of pure water is supplied at the time of performing the said dicing process, the surface of the metal film of a semiconductor substrate may also be exposed to this pure water, and may be affected by it. For example, in a pad made of a metal film, the surface is oxidized, and when the aluminum, copper, or the like is used as the metal film material, corrosion (erosion) c called pitting corrosion may progress (FIG. 2). As a result, a decrease in yield due to poor conduction occurs. It is desired to reduce or prevent the corrosion as described above as much as possible. In recent years, aluminum-copper alloys have become mainstream as pads. According to the inventor's confirmation, when this aluminum-copper alloy was used as a metal film | membrane, it was understood that the progress of corrosion as mentioned above tends to become remarkable. Here, for example, the oxidation (erosion) of the metal film surface is suppressed by using the antioxidant solution disclosed in Japanese Patent Application Laid-Open No. 2009-531512 or Japanese Patent Publication No. 2003-55254 with respect to the metal film surface of the semiconductor substrate. Or it is possible to prevent, but there is always a need to further suppress or prevent such corrosion by oxidation.
그래서, 본 발명은 상기 반도체 기판에 있어서의 특유의 과제의 해결을 감안하여, 그 금속막 표면의 산화에 의한 부식을 더욱 억제 또는 방지하는 산화방지방법 및 산화방지액의 제공을 목적으로 한다. 또한, 본 발명은 산화방지액의 적용에 의해 금속막이나 절연층의 부식이 억제되고, 또한 그 산화방지 효과를 이용하여 특히, 다이싱 공정에 있어서 다량으로 부여되는 물의 영향을 완화시켜 양호한 금속막 표면의 유지를 가능하게 하는 산화방지방법 및 산화방지액의 제공을 목적으로 한다.Accordingly, an object of the present invention is to provide an antioxidant method and an antioxidant solution for further suppressing or preventing corrosion caused by oxidation of the surface of a metal film in view of solving the problems unique to the semiconductor substrate. In addition, the present invention suppresses the corrosion of the metal film and the insulating layer by applying the antioxidant solution, and also utilizes the antioxidant effect to mitigate the effect of water imparted in a large amount in the dicing step, thereby providing a favorable metal film. It is an object of the present invention to provide an anti-oxidation method and an anti-oxidant liquid which enable the maintenance of the surface.
상기 과제는 하기의 수단에 의해 해결되었다.The problem has been solved by the following means.
상기 과제의 해결수단인 본 발명의 금속막 표면의 산화방지방법은 반도체 기판의 금속막 표면을 산화방지액에 의해 처리함에 있어서, 상기 산화방지액으로서 물에 적어도 인 함유 화합물 및 염기성 화합물을 함유시켜 pH를 6∼10으로 조정한 것을 사용하는 것을 특징으로 한다.The oxidation prevention method of the metal film surface of this invention which is the solution of the said subject is made by containing at least a phosphorus containing compound and a basic compound in water as said antioxidant liquid in treating the metal film surface of a semiconductor substrate with an antioxidant solution. It is characterized by using what adjusted pH to 6-10.
또한, 본 발명의 산화방지방법은 상기 산화방지액 중에 방미·방균제를 포함하는 것이 바람직하다.Moreover, it is preferable that the antioxidant method of this invention contains an antimicrobial and antibacterial agent in the said antioxidant liquid.
또한, 본 발명의 산화방지방법은 상기 방미·방균제가 페놀 구조, 피리딘 구조, 트리아진 구조, 모르폴린 구조, 이소티아졸린 구조, 피리디늄 구조, 4급 암모늄 구조 중 어느 하나를 포함하는 화합물인 것이 바람직하다.In addition, the anti-oxidation method of the present invention is a compound in which the anti-bacterial and antibacterial agent includes any one of a phenol structure, a pyridine structure, a triazine structure, a morpholine structure, an isothiazoline structure, a pyridinium structure and a quaternary ammonium structure. It is preferable.
또한, 상기 인 함유 화합물이 무기 인 화합물 또는 유기 인 화합물인 것이 바람직하다.Moreover, it is preferable that the said phosphorus containing compound is an inorganic phosphorus compound or an organic phosphorus compound.
또한, 본 발명의 산화방지방법은 상기 인 함유 화합물이 인산 화합물인 것이 바람직하다.Moreover, in the antioxidant method of this invention, it is preferable that the said phosphorus containing compound is a phosphoric acid compound.
또한, 본 발명의 산화방지방법은 상기 산화방지액에 유기 카르복실산 화합물을 더 함유시키는 것이 바람직하다.Moreover, it is preferable that the antioxidant method of this invention contains an organic carboxylic acid compound further in the said antioxidant liquid.
또한, 본 발명의 산화방지방법은 상기 염기성 화합물이 제4급 아민 화합물 또는 알카놀아민 화합물로 이루어지는 군으로부터 선택되는 적어도 하나의 화합물인 것이 바람직하다.In the antioxidant method of the present invention, the basic compound is preferably at least one compound selected from the group consisting of quaternary amine compounds or alkanolamine compounds.
또한, 본 발명의 산화방지방법은 상기 유기 카르복실산 화합물이 시트르산, 락트산, 아세트산, 프로피온산, 말산, 주석산, 말론산, 옥살산, 숙신산, 글루콘산, 글리콜산, 디글리콜산, 말레산, 벤조산, 프탈산, 살리실산, 살리실히드록삼산 및 프탈히드록삼산으로 이루어지는 군으로부터 선택된 적어도 하나의 화합물인 것이 바람직하다.In addition, the antioxidant method of the present invention is the organic carboxylic acid compound is citric acid, lactic acid, acetic acid, propionic acid, malic acid, tartaric acid, malonic acid, oxalic acid, succinic acid, gluconic acid, glycolic acid, diglycolic acid, maleic acid, benzoic acid, It is preferable that it is at least 1 compound chosen from the group which consists of a phthalic acid, salicylic acid, salicylic hydroxamic acid, and phthal hydroxamic acid.
또한, 본 발명의 산화방지방법은 상기 산화방지액에 의한 처리를 다이싱 공정 전에 실시하는 것이 바람직하다.Moreover, it is preferable that the antioxidant method of this invention performs the process by the said antioxidant liquid before a dicing process.
또한, 본 발명의 산화방지방법은 반도체 기판에 대하여 플라즈마 에칭을 행하는 에칭 공정 및/또는 반도체 기판 상의 레지스트에 대하여 애싱을 행하는 애싱 공정에 있어서, 상기 반도체 기판 상에 형성된 플라즈마 에칭 잔사 및/또는 애싱 잔사를 세정하는 세정 공정 후에 상기 산화방지액에 의한 처리를 실시하는 것이 바람직하다.Further, the anti-oxidation method of the present invention is a plasma etching residue and / or ash residue formed on the semiconductor substrate in an etching step of performing plasma etching on a semiconductor substrate and / or an ashing process of ashing on a resist on the semiconductor substrate. It is preferable to perform the process by the said antioxidant liquid after the washing | cleaning process of washing | cleaning.
또한, 본 발명의 산화방지방법은 상기 금속막이 알루미늄, 구리 및 알루미늄-구리 합금으로 이루어지는 군으로부터 선택되는 것이 바람직하다.In addition, the anti-oxidation method of the present invention is preferably selected from the group wherein the metal film is made of aluminum, copper and aluminum-copper alloy.
상기 과제의 해결수단인 본 발명의 산화방지액은 반도체 기판의 금속막 표면을 처리하는 산화방지액으로서 물과 인 함유 화합물 및 염기성 화합물을 함유시켜 pH를 6∼10으로 조정한 것이다.The antioxidant solution of the present invention, which is a solution to the above problem, is to adjust the pH to 6 to 10 by containing water, a phosphorus-containing compound and a basic compound as an antioxidant to treat the metal film surface of the semiconductor substrate.
또한, 본 발명의 산화방지액은 방미·방균제를 더 포함하는 것이 바람직하다.Moreover, it is preferable that the antioxidant liquid of this invention further contains an antiseptic and antibacterial agent.
또한, 본 발명의 산화방지액은 유기 카르복실산 화합물을 더 포함하는 것이 바람직하다.Moreover, it is preferable that the antioxidant liquid of this invention contains an organic carboxylic acid compound further.
또한, 본 발명의 산화방지액은 pH가 6∼8인 것이 바람직하다.Moreover, it is preferable that pH of the antioxidant liquid of this invention is 6-8.
(발명의 효과)(Effects of the Invention)
본 발명의 산화방지방법 및 산화방지액에 의하면, 반도체 기판의 금속막 표면의 산화에 의한 부식(침식)을 억제 또는 방지할 수 있다. 또한, 산화방지액의 적용에 의해 금속막이나 절연층의 부식이 억제되고, 또한 그 산화방지 효과를 이용하여 특히, 다이싱 공정에 있어서 다량으로 부여되는 물의 영향을 완화시켜 양호한 금속막 표면의 유지를 가능하게 하는 우수한 효과를 나타낸다.According to the antioxidant method and the antioxidant solution of the present invention, corrosion (erosion) due to oxidation of the metal film surface of the semiconductor substrate can be suppressed or prevented. In addition, the application of the antioxidant solution suppresses the corrosion of the metal film and the insulating layer, and furthermore, by utilizing the antioxidant effect, the effect of water imparted in a large amount in the dicing process is alleviated, thereby maintaining a good metal film surface. It shows an excellent effect of enabling.
도 1a는 본 발명의 방법을 적용하는 제1실시형태로서 반도체 소자의 제조 과정의 일부를 모식적으로 나타낸 공정 단면도(그 1)이다.
도 1b는 본 발명의 방법을 적용하는 제1실시형태로서 반도체 소자의 제조 과정의 일부를 모식적으로 나타낸 공정 단면도(그 2)이다.
도 1c는 본 발명의 방법을 적용하는 제1실시형태로서 반도체 소자의 제조 과정의 일부를 모식적으로 나타낸 공정 단면도(그 3)이다.
도 1d는 본 발명의 방법을 적용하는 제1실시형태로서 반도체 소자의 제조 과정의 일부를 모식적으로 나타낸 공정 단면도(그 4)이다.
도 2는 다이싱 공정을 거친 일반적인 반도체 기판의 금속막의 부식(침식) 상태를 설명하는 단면도이다.FIG. 1A is a cross-sectional view (part 1) schematically showing part of a manufacturing process of a semiconductor device as a first embodiment to which the method of the present invention is applied.
FIG. 1B is a cross-sectional view (part 2) schematically showing a part of a manufacturing process of a semiconductor device as a first embodiment to which the method of the present invention is applied.
FIG. 1C is a cross-sectional view (part 3) schematically showing a part of the manufacturing process of a semiconductor device as a first embodiment to which the method of the present invention is applied.
FIG. 1D is a cross sectional view (No. 4) schematically showing part of the manufacturing process of a semiconductor device as a first embodiment to which the method of the present invention is applied.
2 is a cross-sectional view illustrating a corrosion (erosion) state of a metal film of a general semiconductor substrate which has been subjected to a dicing step.
본 발명의 금속막 표면의 산화방지방법은 반도체 기판의 금속막 표면을 산화방지액에 의해 처리함에 있어서, 상기 산화방지액(린스액)으로서 물(a)에 적어도 염기성 화합물(b) 및 인 함유 화합물(c)을 함유시켜 pH를 6∼10으로 조정한 수용액을 사용하는 것을 특징으로 한다. 상기 pH가 조정되고 특유한 성분을 함유하는 수용액은 반도체 기판의 금속막 표면을 부식시키지 않고, 또한 높은 산화방지성을 나타낸다. 특히, 다이싱 공정에 있어서 부여되는 다량의 물의 영향을 저감시키고 금속막 표면의 부식을 효과적으로 억제 또는 방지한다. 이 이유에 대해서는 미해명의 부분을 포함하지만 이하와 같이 추정된다.The antioxidant method of the metal film surface of this invention contains at least a basic compound (b) and phosphorus in water (a) as said antioxidant liquid (rinse liquid) in treating the metal film surface of a semiconductor substrate with antioxidant liquid. It is characterized by using the aqueous solution containing compound (c) and adjusting the pH to 6-10. The aqueous solution containing the said pH adjusted and containing a unique component does not corrode the metal film surface of a semiconductor substrate, and shows high antioxidant property. In particular, the influence of a large amount of water imparted in the dicing step is reduced and the corrosion of the metal film surface is effectively suppressed or prevented. The reason for this is included as follows, but is estimated as follows.
우선, 산화방지액에 함유되는 인 함유 화합물이 금속막 표면에 보호막을 형성하는 작용을 한다고 생각된다. 전형적으로는 알루미늄이나 구리 또는 그 합금 표면에 있어서 상기 인 함유 화합물이 작용함으로써 특유한 부동태막이 형성되고, 그 후에 물과의 접촉에 의해서도 산화의 진행이 억제되는 것이 열거된다. 또한, 본 발명자들은 상기 인 함유 화합물이 염기성 화합물의 공존에 의해 그 액 중의 pH가 특정 범위로 조정됨으로써, 특히, 높은 금속 표면의 보호 작용과 저에칭능이 양립하는 영역이 존재하는 것을 발견했다. 이하에, 본 발명의 바람직한 실시형태에 대해서 일부 도면을 포함시켜 상세하게 설명한다. 단, 이것에 의해, 본 발명이 한정되어 해석되지 않는다.First, it is thought that the phosphorus containing compound contained in antioxidant liquid acts to form a protective film on the metal film surface. Typically, the phosphorus-containing compound acts on the surface of aluminum, copper, or an alloy thereof to form a passivation film peculiar to that, and then the progress of oxidation is also suppressed by contact with water. In addition, the present inventors have found that the phosphorus-containing compound is coexisted with a basic compound to adjust the pH in the liquid to a specific range, so that a region in which both the protective action and the low etching ability of a high metal surface are compatible exists. EMBODIMENT OF THE INVENTION Below, preferable embodiment of this invention is described in detail including some drawing. However, this invention is limited and is not interpreted by this.
본 발명의 바람직한 실시형태에 의하면, 알루미늄이나 구리 또는 그 합금 표면에 수nm 이상의 부동태막층을 형성할 수 있고, 그것에 의해 산화를 방지할 수 있다. 이 부동태막의 존재는 에칭 ESCA나 TEM 등으로 확인할 수 있고, 또한 부동태막의 산화방지 효과는 수중에 있어서의 개회로 전위의 상승으로 확인할 수 있다.According to a preferred embodiment of the present invention, a passivation film layer of several nm or more can be formed on the surface of aluminum, copper or an alloy thereof, whereby oxidation can be prevented. The presence of this passivation film can be confirmed by etching ESCA, TEM, or the like, and the anti-oxidation effect of the passivation film can be confirmed by an increase in the open circuit potential in water.
[산화방지액][Antioxidant]
(물)(water)
본 발명의 산화방지액은 용매로서 물을 함유한다. 물의 함유량은 산화방지액 전체 질량에 대하여 60∼99.9질량%인 것이 바람직하고, 90∼99.9질량%인 것이 보다 바람직하다. 상술한 바와 같이, 물을 주성분(50질량% 이상)으로 하는 산화방지액을 특히, 수계 산화방지액이라고 하는 경우가 있다. 물로서는 본 발명의 효과를 손상시키지 않는 범위로 용해 성분을 포함하는 수성매체이어도 좋고, 또는 불가피하게 미량 혼합 성분을 포함하고 있어도 좋다. 그 중에서도, 증류수나 이온교환수 또는 초순수라고 하는 정화 처리를 실시한 물이 바람직하고, 반도체 제조에 사용되는 초순수를 사용하는 것이 특히 바람직하다.The antioxidant solution of the present invention contains water as a solvent. It is preferable that it is 60-99.9 mass% with respect to the total mass of antioxidant liquid, and, as for content of water, it is more preferable that it is 90-99.9 mass%. As mentioned above, the antioxidant liquid which has water as a main component (50 mass% or more) may be called especially an aqueous antioxidant liquid. As water, the aqueous medium containing a dissolution component may be sufficient as the range which does not impair the effect of this invention, or it may inevitably contain a trace amount mixed component. Especially, the water which performed the purification process of distilled water, ion-exchange water, or ultrapure water is preferable, and it is especially preferable to use the ultrapure water used for semiconductor manufacture.
(인 함유 화합물)(Phosphorus containing compound)
본 발명의 산화방지액은 적어도 하나의 인 함유 화합물(인 원자를 분자내에 갖는 화합물)을 함유한다. 인 함유 화합물은 무기 인 화합물이어도 유기 인 화합물이어도 좋고, 그 중에서도 인산 화합물인 것이 바람직하다. 여기서, 인산 화합물이란 인산, 폴리 인산, 포스폰산 또는 그것의 염을 포함하는 개념이다. 또한, 본 명세서에 있어서 화합물이라고 하는 경우에는 상기 화합물 그 자체에 추가하여 그 염, 그 이온을 포함하는 의미로 사용하고, 전형적으로는 상기 화합물 및/또는 그 염을 의미한다. 구체적으로는, 인산, 폴리 인산 이외에 메타 인산, 울트라 인산, 아인산, 5산화 2인, 차아인산도 사용할 수 있다. 폴리 인산의 경우에는 반복 구조가 2∼5개가 바람직하고, 메타 인산의 경우에는 3∼5개가 바람직하다.The antioxidant liquid of this invention contains at least 1 phosphorus containing compound (compound which has a phosphorus atom in a molecule). The phosphorus-containing compound may be an inorganic phosphorus compound or an organic phosphorus compound, and in particular, it is preferable that it is a phosphoric acid compound. Here, a phosphoric acid compound is a concept containing phosphoric acid, polyphosphoric acid, phosphonic acid, or its salt. In addition, in this specification, a compound is used in the meaning containing the salt and its ion in addition to the said compound itself, and typically means the said compound and / or its salt. Specifically, in addition to phosphoric acid and polyphosphoric acid, metaphosphoric acid, ultra phosphoric acid, phosphorous acid, diphosphate pentoxide, hypophosphorous acid can also be used. In the case of polyphosphoric acid, 2-5 pieces are preferable, and in the case of metaphosphoric acid, 3-5 pieces are preferable.
유기 인 화합물에는 메틸포스폰산, 에틸포스폰산, 프로필포스폰산, 부틸포스폰산, 포스카르넷(foscarnet), 벤질포스폰산, 아미노메틸포스폰산, 메틸렌디포스폰산, 1-히드록시에탄-1,1-비스(포스폰산) 등이 열거된다.Organophosphorus compounds include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, foscarnet, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1 -Bis (phosphonic acid) and the like.
상기 인 함유 화합물은 1종 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The said phosphorus containing compound can be used individually by 1 type or in mixture of 2 or more types.
상기 인 함유 화합물은 산화방지액 전체량에 대하여 바람직하게는 0.001∼10질량%로 가해지고, 보다 바람직하게는 0.01∼5질량%로 가해지고, 특히 바람직하게는 0.1∼2.5질량%로 가해진다. 인 함유 화합물의 양을 상기 하한값 이상으로 함으로써 1nm 이상의 보호막 형성을 행할 수 있는 관점에서 바람직하다. 한편, 상기 상한값 이하로 함으로써 과잉의 금속막 에칭을 억제할 수 있는 관점에서 바람직하다.The phosphorus-containing compound is preferably added at 0.001 to 10% by mass, more preferably at 0.01 to 5% by mass, and particularly preferably at 0.1 to 2.5% by mass, based on the total amount of the antioxidant solution. It is preferable from a viewpoint that 1 nm or more of protective film formation can be performed by making quantity of a phosphorus containing compound more than the said lower limit. On the other hand, it is preferable from the viewpoint that excessive metal film etching can be suppressed by using below the said upper limit.
<염기성 화합물><Basic compound>
본 발명의 산화방지액은 염기성 화합물을 포함한다. 염기성 화합물은 염기성 유기 화합물이어도 염기성 무기 화합물이어도 좋지만, 염기성 유기 화합물인 것이 바람직하다. 염기성 유기 화합물의 구성 원소로서 탄소 및 질소를 갖는 것이 바람직하고, 아미노기를 갖는 것이 보다 바람직하다. 구체적으로는, 염기성 유기 화합물은 유기 아민 및 제4급 암모늄 수산화물로 이루어지는 군으로부터 선택된 적어도 하나의 화합물인 것이 바람직하다. 또한, 유기 아민이란 구성 원소로서 탄소를 포함하는 아민을 의미한다.The antioxidant solution of the present invention contains a basic compound. Although a basic organic compound or a basic inorganic compound may be sufficient as a basic compound, it is preferable that it is a basic organic compound. It is preferable to have carbon and nitrogen as a structural element of a basic organic compound, and it is more preferable to have an amino group. Specifically, the basic organic compound is preferably at least one compound selected from the group consisting of organic amines and quaternary ammonium hydroxides. In addition, an organic amine means the amine containing carbon as a structural element.
염기성 유기 화합물의 탄소수는 4∼30개인 것이 바람직하고, 비점 또는 물에 대한 용해도의 관점에서 6∼16개인 것이 보다 바람직하다.It is preferable that carbon number of a basic organic compound is 4-30, and it is more preferable that it is 6-16 from a viewpoint of a boiling point or solubility to water.
유기 아민으로서는:Organic amines include:
·에탄올아민, 디에탄올아민, 트리에탄올아민, 제3부틸디에탄올아민, 이소프로판올아민, 2-아미노-1-프로판올아민, 3-아미노-1-프로판올아민, 이소부탄올아민, 2-아미노에탄올아민, 2-아미노(2-에톡시에탄올)아민, 2-아미노(2-에톡시프로판올)아민, 디에틸렌글리콜아민, 디글리콜아민, N-히드록실에틸피페라진 등의 알카놀아민;Ethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanolamine, 3-amino-1-propanolamine, isobutanolamine, 2-aminoethanolamine, 2 Alkanolamines such as amino (2-ethoxyethanol) amine, 2-amino (2-ethoxypropanol) amine, diethylene glycolamine, diglycolamine, and N-hydroxyethylpiperazine;
·에틸아민, 벤질아민, 디에틸아민, n-부틸아민, 3-메톡시프로필아민, tert-부틸아민, n-헥실아민, 시클로헥실아민, n-옥틸아민, 2-에틸헥실아민, o-크실렌디아민, m-크실릴렌디아민, 1-메틸부틸아민, 에틸렌디아민(EDA), 1,3-프로판디아민, 2-아미노벤질아민, N-벤질에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민 등의 수산기를 갖지 않는 유기 아민이 포함된다.Ethylamine, benzylamine, diethylamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, o- Xylenediamine, m-xylylenediamine, 1-methylbutylamine, ethylenediamine (EDA), 1,3-propanediamine, 2-aminobenzylamine, N-benzylethylenediamine, diethylenetriamine, triethylenetetramine Organic amine which does not have a hydroxyl group, such as these, is contained.
제4급 암모늄 수산화물로서는 테트라알킬암모늄 수산화물이 바람직하고, 저급(탄소수 1∼4개) 알킬기로 치환된 테트라알킬암모늄 수산화물이 보다 바람직하고, 구체적으로는 테트라메틸암모늄 히드록시드(TMAH), 테트라에틸암모늄 히드록시드(TEAH), 테트라프로필암모늄 히드록시드(TPAH), 테트라부틸암모늄 히드록시드(TBAH) 등이 열거된다. 또한, 제4급 암모늄 수산화물로서 트리메틸히드록시에틸암모늄 히드록시드(콜린), 메틸트리(히드록시에틸)암모늄 히드록시드, 테트라(히드록시에틸)암모늄 히드록시드, 벤질트리메틸암모늄 히드록시드(BTMAH) 등도 열거된다. 그것에 추가해서 암모늄 수산화물과 1개 또는 그 이상의 제4급 암모늄 수산화물을 조합시켜 사용할 수 있다. 이들 중에서도 TMAH, TEAH, TPAH, TBAH, 콜린이 보다 바람직하고, TMAH, TBAH가 특히 바람직하다.As quaternary ammonium hydroxide, tetraalkylammonium hydroxide is preferable, tetraalkylammonium hydroxide substituted with a lower (C1-C4) alkyl group is more preferable, specifically, tetramethylammonium hydroxide (TMAH) and tetraethyl Ammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH) and the like. Further, as the quaternary ammonium hydroxide, trimethylhydroxyethylammonium hydroxide (choline), methyltri (hydroxyethyl) ammonium hydroxide, tetra (hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide ( BTMAH) and the like. In addition to that, it is possible to use a combination of ammonium hydroxide and one or more quaternary ammonium hydroxides. Among these, TMAH, TEAH, TPAH, TBAH and choline are more preferable, and TMAH and TBAH are particularly preferable.
무기 염기로서는 특별히 한정되지 않지만, KOH, NaOH, LiOH 등이 열거되고, 그 중에서도 KOH가 바람직하다.Although it does not specifically limit as an inorganic base, KOH, NaOH, LiOH, etc. are mentioned, Especially, KOH is preferable.
상기 염기성 화합물은 1종 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다.The said basic compound can be used individually by 1 type or in mixture of 2 or more types.
본 발명의 산화방지액에 있어서, 염기성 화합물의 함유량은 0.001∼20질량%인 것이 바람직하고, 0.01∼10질량%인 것이 보다 바람직하고, 0.1∼5질량%인 것이 특히 바람직하다. 염기성 화합물의 양을 상기 하한값 이상, 상한값 이하로 함으로써 적절한 pH로 조정할 수 있는 관점에서 바람직하다.In the antioxidant solution of the present invention, the content of the basic compound is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, particularly preferably 0.1 to 5% by mass. It is preferable from a viewpoint which can adjust to appropriate pH by making quantity of a basic compound into the said lower limit or more and an upper limit or less.
<pH><pH>
본 발명의 산화방지액의 pH가 6∼10으로 조정되어 있고, pH가 6∼9인 것이 바람직하고, pH가 6∼8인 것이 보다 바람직하다. pH를 상기 범위로 함으로써 산화방지액을 실질적으로 중성 또는 약알칼리성으로 할 수 있고, 금속막이나 절연층의 내부식성을 확보할 수 있다. 본 발명에 있어서는 특별히 언급하지 않는 한, pH는 실시예에 나타낸 조건으로 측정한 값을 말한다. 산화방지액을 소정의 pH로 조정하기 위해서는 염기성 화합물의 첨가량을 조절한 적정에 의해 행할 수 있다.It is preferable that pH of the antioxidant liquid of this invention is adjusted to 6-10, pH is 6-9, and it is more preferable that pH is 6-8. By setting the pH to the above range, the antioxidant can be made substantially neutral or weakly alkaline, and the corrosion resistance of the metal film and the insulating layer can be ensured. In the present invention, unless specifically mentioned, pH refers to the value measured on the conditions shown in the Example. In order to adjust antioxidant liquid to predetermined pH, it can carry out by titration which adjusted the addition amount of a basic compound.
(카르복실산 화합물)(Carboxylic acid compound)
본 발명의 산화방지액은 상기의 각 성분 이외에 카르복실산 화합물을 더 함유하는 것이 바람직하다. 유기 카르복실산 화합물로서는 시트르산, 락트산, 아세트산, 프로피온산, 말산, 주석산, 말론산, 옥살산, 숙신산, 글루콘산, 글리콜산, 디글리콜산, 말레산, 벤조산, 프탈산, 살리실산, 살리실히드록삼산, 프탈히드록삼산, 포름산 또는 이들의 염이 열거되고, 그 중에서도 시트르산, 락트산, 아세트산, 말산, 주석산, 말론산, 살리실히드록삼산, 프탈히드록삼산이 바람직하다. 상기 유기 카르복실산 화합물은 1종 단독으로 또는 2종 이상을 혼합하여 사용될 수 있다. 본 발명의 산화방지액에 있어서, 유기 카르복실산 화합물의 함유량은 방식성의 관점에서 0.001∼10질량%인 것이 바람직하고, 0.01∼5질량%인 것이 보다 바람직하고, 0.01∼3질량%인 것이 특히 바람직하다.It is preferable that the antioxidant liquid of this invention contains a carboxylic acid compound further in addition to each said component. Examples of the organic carboxylic acid compound include citric acid, lactic acid, acetic acid, propionic acid, malic acid, tartaric acid, malonic acid, oxalic acid, succinic acid, gluconic acid, glycolic acid, diglylic acid, maleic acid, benzoic acid, phthalic acid, salicylic acid, salicylic acid, Phthalic acid, formic acid or salts thereof are listed, and citric acid, lactic acid, acetic acid, malic acid, tartaric acid, malonic acid, salicylic acid, and phthalic acid are preferable. The said organic carboxylic acid compound can be used individually by 1 type or in mixture of 2 or more types. In the antioxidant solution of the present invention, the content of the organic carboxylic acid compound is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass from the viewpoint of anticorrosiveness. desirable.
(방미·방균제)(Flavor, Antibacterial)
본 발명에 있어서는 방미·방균제를 더 함유하는 것이 바람직하다. 이것은 본 발명의 산화방지액 또는 이것을 사용한 산화방지방법이 실질적으로 중성 영역에서 규정된다는 것과 밀접히 관련된다. 즉, 강한 산성이나 알칼리성 하에서는 현재화하기 어려운 현상으로 중성 영역에서는 세균이나 곰팡이가 발생하기 쉬워 그 액물성에 영향을 주는 경우가 있다. 또한, 반대로 말하면, 중성 영역이기 때문에 효과적인 방미·항균제를 적용할 수 있어 그 높은 효과를 발휘할 수 있다. 또한, 이러한 방미·항균제의 첨가에 의해서도, 본 발명에 있어서 바람직한 산화방지 효과를 발휘하는 중성 영역이 유지되는 것이 바람직하다. 이러한 상황을 고려하여, 본 발명에서는 방미·방균제로서 페놀 구조, 피리딘 구조, 트리아진 구조, 모르폴린 구조, 이소티아졸린 구조, 피리디늄 구조, 4급 암모늄 구조 중 어느 하나를 포함하는 화합물을 사용하는 것이 바람직하다.In the present invention, it is preferable to further contain an antiseptic and antibacterial agent. This is closely related to the antioxidant solution of the present invention or the antioxidant method using the same, which is substantially defined in the neutral region. That is, a phenomenon that is difficult to present under strong acidity or alkalinity, and bacteria and mold are likely to occur in the neutral region, which may affect the liquidity. In addition, on the contrary, since it is a neutral region, an effective antimicrobial and antibacterial agent can be applied and the high effect can be exhibited. In addition, it is preferable that the neutral region which exhibits a preferable antioxidant effect is maintained also by addition of such an antiseptic and antibacterial agent. In view of such a situation, in the present invention, a compound containing any one of a phenol structure, a pyridine structure, a triazine structure, a morpholine structure, an isothiazoline structure, a pyridinium structure, and a quaternary ammonium structure is used as the anti-bacterial and antibacterial agent. It is desirable to.
방미·방균제의 구체예로서는 2-메틸-4-이소티아졸린-3-온, 1,2-벤조이소티아졸린-3-온, 5-클로로-2-메틸-4-이소티아졸린-3-온, o-페닐페놀, 3-메틸-4-클로로페놀, 2-메르캅토피리딘-N-옥시드나트륨, 헥사하이드로-1,3,5-트리에틸-s-트리아진, p-톨루엔술폰산염, 4-(2-니트로부틸)모르폴린, 4,4'-(2-에틸-2-니트로트리메틸렌)디모르폴린, 염화 테트라메틸암모늄, 염화 도데실피리디늄 등이 열거된다.As a specific example of an antibacterial and antibacterial agent, 2-methyl-4-isothiazolin-3-one, 1,2-benzoisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one On, o-phenylphenol, 3-methyl-4-chlorophenol, 2-mercaptopyridine-N-oxide sodium, hexahydro-1,3,5-triethyl-s-triazine, p-toluenesulfonate , 4- (2-nitrobutyl) morpholine, 4,4 '-(2-ethyl-2-nitrotrimethylene) dimorpholine, tetramethylammonium chloride, dodecylpyridinium chloride, etc. are mentioned.
본 발명에 있어서, 방미·방균제의 함유량은 상술한 상호작용의 점에서 0.001∼10질량%인 것이 바람직하고, 0.01∼5질량%인 것이 보다 바람직하고, 0.01∼3질량%인 것이 특히 바람직하다.In this invention, it is preferable that it is 0.001-10 mass% from the point of the interaction mentioned above, as for content of a fungicide and antibacterial agent, it is more preferable that it is 0.01-5 mass%, and it is especially preferable that it is 0.01-3 mass%. .
또한, 방미·방균제로서 상기 인 함유 화합물이나 염기성 화합물에 해당되는 화합물과 공통되는 것이 포함되지만 이들을 방미·방균제로서 적용하는 것을 방해하지 않는다.Moreover, although the thing common with the said phosphorus containing compound and a compound corresponding to a basic compound is contained as an anti-fog and antimicrobial agent, it does not prevent the application of these as an anti-fog and antimicrobial agent.
(기타 성분)(Other ingredients)
·아미노기 함유 카르복실산 화합물Amino group-containing carboxylic acid compounds
본 발명의 산화방지액은 그 밖에 아미노기 함유 카르복실산 화합물을 함유해도 좋다. 아미노기 함유 카르복실산 화합물은 금속 부식을 효율적으로 방지하는 점에서 바람직하다. 아미노기 함유 카르본 화합물은 아르기닌, 히스티딘, 글루타민, EDTA, DTPA, HIDA가 바람직하고, 아르기닌, 히스티딘이 보다 바람직하다. 이들 아미노기 함유 카르복실산 화합물은 1종 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 본 발명의 산화방지액에 있어서, 아미노기 함유 카르복실산 화합물을 함유하는 경우에 그 첨가량은 적당히 선택될 수 있지만, 본 발명의 산화방지액의 전체 질량에 대하여 약 0.01∼약 5.0질량%인 것이 바람직하고, 0.01∼3질량%인 것이 보다 바람직하다.The antioxidant solution of the present invention may further contain an amino group-containing carboxylic acid compound. An amino group containing carboxylic acid compound is preferable at the point which prevents metal corrosion efficiently. Arginine, histidine, glutamine, EDTA, DTPA, HIDA are preferable, and, as for an amino-group containing carbon compound, arginine and histidine are more preferable. These amino group containing carboxylic acid compounds can be used individually by 1 type or in mixture of 2 or more types. In the antioxidant solution of the present invention, the amount of the amino group-containing carboxylic acid compound may be appropriately selected, but it is preferably about 0.01 to about 5.0% by mass based on the total mass of the antioxidant solution of the present invention. And it is more preferable that it is 0.01-3 mass%.
·계면활성제·Surfactants
또한, 본 발명의 산화방지액은 계면활성제를 함유해도 좋다. 계면활성제로서는 비이온성, 음이온성, 양이온성 계면활성제 및 양성 계면활성제를 사용할 수 있다. 산화방지액 중의 계면활성제의 함유량은 산화방지액의 전체 질량에 대하여 바람직하게는 0.0001∼5질량%이고, 보다 바람직하게는 0.0001∼1질량%이다. 계면활성제를 산화방지액에 첨가함으로써 그 점도를 조정하여 대상물에 대한 젖음성을 개량시킬 수 있기 때문에 바람직하고, 또한 기판이나 절연막 등에 대한 데미지성의 양쪽이 보다 우수하다는 점에서도 바람직하다. 이와 같이, 계면활성제는 일반적으로 상업적으로 입수가능하다. 이들 계면활성제는 단독 또는 복수 조합하여 사용해도 좋다.Moreover, the antioxidant liquid of this invention may contain surfactant. As the surfactant, nonionic, anionic, cationic surfactants and amphoteric surfactants can be used. Content of surfactant in antioxidant liquid becomes like this. Preferably it is 0.0001-5 mass% with respect to the total mass of antioxidant liquid, More preferably, it is 0.0001-1 mass%. It is preferable because the viscosity can be adjusted by adding the surfactant to the antioxidant solution to improve the wettability to the object, and it is also preferable that both of the damage properties to the substrate, the insulating film and the like are more excellent. As such, surfactants are generally commercially available. You may use these surfactant individually or in combination of 2 or more.
·부식방지제Anticorrosive
본 발명의 산화방지액은 복소환 화합물을 함유해도 좋다. 복소환 화합물은 벤조트리아졸 및 그 유도체인 것이 보다 바람직하다. 상기 유도체로서는 5,6-디메틸-1,2,3-벤조트리아졸(DBTA), 1-(1,2-디카르복시에틸)벤조트리아졸(DCEBTA), 1-[N,N-비스(히드록시에틸)아미노메틸]벤조트리아졸(HEABTA), 1-(히드록시메틸)벤조트리아졸(HMBTA)이 바람직하다. 본 발명에 사용되는 부식방지제는 단독으로 사용해도 좋고, 2종 이상 병용해도 좋다. 또한, 본 발명에 사용되는 부식방지제는 정법에 따라서 합성할 수 있는 것 이외에 시판품을 사용해도 좋다. 또한, 부식방지제의 첨가량은 산화방지액 전체량에 대하여 바람직하게는 0.01질량% 이상 0.2질량% 이하이고, 보다 바람직하게는 0.05질량% 이상 0.2질량% 이하이다.The antioxidant solution of the present invention may contain a heterocyclic compound. The heterocyclic compound is more preferably benzotriazole and its derivatives. Examples of the derivative include 5,6-dimethyl-1,2,3-benzotriazole (DBTA), 1- (1,2-dicarboxyethyl) benzotriazole (DCEBTA), and 1- [N, N-bis (hydr) Preferred are hydroxyethyl) aminomethyl] benzotriazole (HEABTA) and 1- (hydroxymethyl) benzotriazole (HMBTA). The corrosion inhibitor used for this invention may be used independently and may be used together 2 or more types. In addition, the corrosion inhibitor used in the present invention may be commercially available in addition to the synthetic method according to the conventional method. The addition amount of the corrosion inhibitor is preferably 0.01% by mass or more and 0.2% by mass or less, more preferably 0.05% by mass or more and 0.2% by mass or less, based on the total amount of the antioxidant solution.
[린스방법][Rinse method]
이어서, 본 발명의 산화방지액의 바람직한 적용방법(린스방법)에 대해서 설명한다. 본 실시형태에 있어서는 상기 산화방지액에 의한 처리를 다이싱 공정 전에 실시하는 것이 바람직하다. 또한, 반도체 기판에 대하여 플라즈마 에칭을 행하는 에칭 공정 및/또는 반도체 기판 상의 레지스트에 대하여 애싱을 행하는 애싱 공정에 있어서, 상기 반도체 기판 상에 형성된 플라즈마 에칭 잔사 및/또는 애싱 잔사를 세정하는 세정 공정 후에 상기 산화방지액에 의한 처리를 실시하는 것이 바람직하다. 이 시기에 본 발명의 산화방지 처리를 실시함으로써, 반도체 기판의 금속막 표면을 다이싱 공정에 있어서의 다량의 물과 접촉에 의한 침식으로부터 효과적으로 보호할 수 있고, 특히, 그 높은 효과가 얻어지는 점에서 바람직하다. 단, 그 시기 이외에 있어서, 상기 산화방지액을 적용하는 것을 방해하지 않는다. 또한, 산화방지액 또는 세정액에 의한 금속막의 「부식」과 다이싱 공정에 있어서의 다량의 물에 의한 「부식」을 구별하여 말할 때에는 후자를 「침식」이라고 하는 경우가 있다.Next, the preferable application method (rinse method) of the antioxidant solution of this invention is demonstrated. In this embodiment, it is preferable to perform the process by the said antioxidant liquid before a dicing process. Further, in the etching step of performing plasma etching on the semiconductor substrate and / or the ashing step of ashing the resist on the semiconductor substrate, after the cleaning step of cleaning the plasma etching residue and / or ashing residue formed on the semiconductor substrate, It is preferable to perform the treatment with the antioxidant solution. By performing the anti-oxidation treatment of the present invention at this time, the surface of the metal film of the semiconductor substrate can be effectively protected from erosion by contact with a large amount of water in the dicing step, and in particular, the high effect is obtained. desirable. However, in addition to that period, application of the antioxidant solution is not prevented. In addition, when distinguishing between the "corrosion" of the metal film by antioxidant liquid or a washing | cleaning liquid, and the "corrosion" by a large amount of water in a dicing process, the latter may be called "erosion".
본 발명의 산화방지액에 의한 처리를 린스 또는 린스 처리라고 하고, 그 산화방지액을 린스액이라고 하는 경우가 있다. 이것은 상기 잔사의 세정 조성물(세정액)과는 별개로, 그것과는 다른 처리액으로서 적용시키는 것을 의미한 것이며, 샴푸 후의 린스와 동일하게 세정 후의 처리액이라는 점을 고려한 호칭이다. 또한, 여기서, 「린스」란 상기 잔사의 세정 후에 그 세정액을 더 씻어내는 것이나(일본특허공개 2007-123787호 공보) 잔사 제거의 효과를 보완하는 의미로 추가 세정하는 것(일본특허공개 2003-5388호 공보)과는 구별된다.The treatment with the antioxidant solution of the present invention may be referred to as a rinse or rinse treatment, and the antioxidant solution may be referred to as a rinse liquid. This means that the residue is applied separately from the cleaning composition (washing liquid) of the residue as a treatment liquid different from that, and is a name considering the treatment liquid after washing in the same manner as the rinse after the shampoo. Here, "rinse" refers to further washing the cleaning solution after washing the residue (Japanese Patent Laid-Open No. 2007-123787) or to further cleaning in order to compensate for the effect of removing the residue (Japanese Patent Laid-Open No. 2003-5388). Call publications).
본 발명의 산화방지액에 의한 처리 전에 다른 약액으로 웨이퍼 전처리를 행해도 좋다. 웨이퍼 전처리 액으로서 알칼리성 수용액이 바람직하고 예컨대, 테트라메틸암모늄 히드록시드(TMAH), 테트라에틸암모늄 히드록시드(TEAH), 테트라프로필암모늄 히드록시드(TPAH), 테트라부틸암모늄 히드록시드(TBAH) 등이 열거된다.You may perform wafer pretreatment with another chemical liquid before the process by the antioxidant liquid of this invention. As the wafer pretreatment liquid, an alkaline aqueous solution is preferable, and for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH) And the like.
본 발명의 산화방지액은 잔사의 세정 조성물(세정액)로서 이용되는 것이 기본적으로 상정되어 있지 않다. 그 이유는 최근 디바이스 구조에는 잔사가 많아 잔사 제거·저금속막 에칭·보호막 형성에 의한 산화방지를 양립할 수 없기 때문에, 세정액과 산화방지액을 2액으로 함으로써 상기 3항목을 달성할 수 있다. 본 발명의 산화방지액과 조합시키는 것이 바람직한 세정액의 처방으로서는 하기의 것이 열거된다.It is not assumed that the antioxidant liquid of this invention is used as the cleaning composition (washing liquid) of a residue. The reason for this is that in recent years, since there are many residues in the device structure, it is not compatible with oxidation removal due to residue removal, low metal film etching, and protective film formation, so that the above three items can be achieved by making the cleaning liquid and the antioxidant liquid into two liquids. The following are listed as prescription of the washing | cleaning liquid which is preferable to combine with antioxidant solution of this invention.
·불소 화합물과 카르복실산을 적어도 물에 함유시킨 세정 조성물Cleaning composition in which a fluorine compound and a carboxylic acid are contained at least in water
·불소 화합물과 아민을 적어도 물에 함유시킨 세정 조성물Cleaning composition containing at least water and a fluorine compound and an amine
·알카놀아민과 히드록실아민을 적어도 물에 함유시킨 세정 조성물Cleaning composition comprising at least water of alkanolamine and hydroxylamine
·유기용제로 이루어지는 세정 조성물Cleaning composition consisting of organic solvents
·히드록실아민과 카르복실산과 물을 포함하는 세정 조성물Cleaning composition comprising hydroxylamine, carboxylic acid and water
본 발명의 산화방지액과 상기 세정 조성물을 조합하여 사용함으로써 잔사 제거와 금속막의 저에칭능과 산화방지라는 효과가 향상되는 점에서 바람직하다. 또한, 상기 세정 조성물의 조성(질량%)은 임의로 설정할 수 있고 예컨대, 그 pH에 맞춰서 산성 화합물과 염기성 화합물을 배합하면 좋다.By using the antioxidant solution of the present invention in combination with the cleaning composition, the effect of removing residues, the low etching ability of the metal film, and the antioxidant is improved. In addition, the composition (mass%) of the said cleaning composition can be arbitrarily set, for example, What is necessary is just to mix | blend an acidic compound and a basic compound according to the pH.
본 발명의 산화방지액은 특정 린스방법에 따르지 않고, 각종 실시형태에 적합하게 사용할 수 있다. 예컨대, 사용장치는 매엽식이어도 배치식이어도 어느 것이어도 좋다. 린스시의 온도는 실온 이상이 바람직하다. 처리 시간은 30초∼10분이 바람직하다. 적용량은 적당히 선택할 수 있다.The antioxidant liquid of this invention can be used suitably for various embodiment, without following a specific rinsing method. For example, the use apparatus may be either a single-leaf type or a batch type. As for the temperature of rinsing, room temperature or more is preferable. The treatment time is preferably 30 seconds to 10 minutes. The application amount can be suitably selected.
[반도체 소자의 제조][Manufacture of Semiconductor Device]
이어서, 본 발명의 산화방지액을 바람직하게 적용할 수 있는 반도체 소자의 구조 및 그 제조 과정 중 일례에 대해서 도 1(도 1a∼1-4)을 사용하여 설명한다. 동 도는 본 실시형태에 의거한 반도체 소자의 제조 과정 중 일부의 개요를 나타낸 공정 단면도이다. 본 실시형태에 있어서는 소정의 구조로 반도체 기판을 구성하고, 그 최상부에 형성된 패드(패드 전극)(5)를 노출시키는 개구부(H)가 형성되어 있다(도 1d 참조). 그 후의 회로기판에의 실장에는 이 패드의 부분을 단자로 해서 본딩 와이어 등이 접속된다. 본 실시형태에 있어서는 그 다이싱 공정에 앞서 상기 노출된 패드의 금속막 표면(55)에 부동태막을 형성하여 산화 부식으로부터 보호하는 것이다. 또한, 본 명세서에 있어서 반도체 기판이란 반도체 소자를 제조하는 중간체(전구체)의 총칭으로서 사용되고, 실리콘 웨이퍼뿐만 아니라 그것에 절연막이나 전극 등이 부착된 실장 전의 중간 제품을 포함하는 의미이다.Next, an example of the structure of the semiconductor element to which the antioxidant solution of the present invention can be preferably applied and one example of a manufacturing process thereof will be described using FIG. 1 (FIGS. 1A to 1-4). The figure is a process cross section which showed the outline | summary of a part of the manufacturing process of the semiconductor element based on this embodiment. In this embodiment, the semiconductor substrate is constituted by a predetermined structure, and an opening H is formed to expose the pad (pad electrode) 5 formed at the top thereof (see FIG. 1D). Subsequently, bonding wires or the like are connected to the circuit boards with the pads as terminals. In this embodiment, a passivation film is formed on the exposed
반도체 기판 상에 형성된 다층배선 구조에 있어서는 적층된 층간 절연막 중에 배선 패턴이 형성되어 있다. 또한, 배선패턴 사이를 접속하는 비어가 층간 절연막 중에 적당히 형성되어 있다. 도 중의 공정(a)에는 (도 1a), 패드까지 형성된 다층배선 구조의 최상부의 일례를 나타낸 것이다. 도시한 바와 같이, 반도체 기판(도시생략) 상에 형성된 층간 절연막(1) 중에는 배선 패턴(7)이 형성되어 있다. 배선 패턴(7)은 TiN이나 Ti막 등의 배리어 메탈막(71)과 배리어 메탈막(71)에 덮여진 알루미늄(Al)막(72)을 가지고 있다. 그 옆에는 배리어 메탈막(81)에 덮여진 Al막(82)으로 구성된 배선 패턴(8)이 도시되어 있지만, 이 단면에 있어서는 패드와 접속되어 있지 않다. 또한, 층간 절연막(1 및 2)도 단면을 나타내고 있지만 도면의 번잡화를 피하여 해칭이 되어 있지 않다.In the multilayer wiring structure formed on the semiconductor substrate, the wiring pattern is formed in the laminated interlayer insulating film. In addition, a via for connecting the wiring patterns is appropriately formed in the interlayer insulating film. Step (a) in FIG. 1 shows an example of the uppermost part of the multilayer wiring structure formed up to the pad (FIG. 1A). As shown, the
배선 패턴(7)이 형성된 층간 절연막(1) 상에는 층간 절연막(2)이 형성되어 있다. 층간 절연막(2) 중에는 배선 패턴(7)에 접속된 비어(6)가 형성되어 있다. 비어(6)는 질화 티타늄막 등의 배리어 메탈막(61)과 배리어 메탈막(61)에 덮여진 텅스텐막(62)을 가지고 있다. 비어(6)가 형성된 층간 절연막(2) 상에는 비어(6)를 통하여 배선 패턴(7)에 접속된 패드(패드 전극)(5)가 형성되어 있다. 패드(5)는 순차 적층된 밀착막(51)과 Al-Cu막(52)과 밀착막(52)을 가지고 있다. 밀착막(51, 53)은 티타늄/질화 티타늄의 적층 구조 또는 질화 티타늄의 단층 구조를 가지고 있다. 이와 같이, 패드(5)가 형성된 층간 절연막(2) 상에 예컨대, 고밀도 플라즈마 CVD법에 의해 실리콘 산화막(3)을 형성한다(공정 (b) 참조).An interlayer insulating
이어서, 실리콘 산화막(3) 상에 예컨대, 플라즈마 CVD법에 의해 실리콘 질화막으로 이루어지는 패시베이션막(4)을 형성한다(공정 (c) 참조).Subsequently, a
이어서, 패시베이션막(4) 상에 포토리소그래피에 의해 패드(5)에 도달하는 개구부의 형성 영역을 노출하는 포토레지스트막(도시생략)을 형성한다. 이어서, 이 포토레지스트막을 마스크로 해서 플라즈마를 사용한 드라이 에칭에 의해 패시베이션막(4) 및 실리콘 산화막(3)을 에칭한다. 이 때, 패드(5)의 밀착막(51) 및 Al-Cu막(52)의 상부도 에칭될 수 있다. 이와 같이, 패시베이션막(4) 및 실리콘 산화막(3)에 패드(5)를 노출하는 개구부(H)를 형성한다(공정 (d) 참조). 패시베이션막(4) 및 실리콘 산화막(3)의 드라이 에칭은 각각 공지의 방법을 사용하여 행할 수 있다.Next, a photoresist film (not shown) is formed on the
이어서, 플라즈마를 사용한 애싱에 의해 마스크로서 사용한 포토레지스트막을 제거한다(공정 (e) 참조). 포토레지스트막의 애싱은 공지의 방법을 사용하여 행할 수 있다. 개구부(H)를 형성하기 위한 포토레지스트막의 형성, 패시베이션막(4) 및 실리콘 산화막(3)의 드라이 에칭 및 포토레지스트막을 제거하기 위한 애싱에 있어서는 개구부(H) 주변의 표면을 포함하는 기판 표면에 잔사(플라즈마 에칭 잔사)(z)가 부착된다. 이 잔사(z)는 변질된 포토레지스트막, 패시베이션막(4), 실리콘 산화막(3) 및 밀착막(51), Al-Cu막(52) 등에 유래한다. 도 중에는 잔사의 종류에 따라 구별하여 나타내지 않는다.Next, the photoresist film used as a mask is removed by ashing using plasma (see step (e)). Ashing of the photoresist film can be performed using a well-known method. In the formation of the photoresist film for forming the opening H, the dry etching of the
여기서, 포토레지스트막을 제거하기 위한 애싱 후에, 잔사 세정액에 의해 패드(52)를 노출하는 개구부(H)까지 형성된 반도체 기판을 세정한다(공정 (f)). 이와 같이, 개구부(H)의 내벽 및 저면(Al-Cu막 표면)이 세정되어 거기에 부착된 잔사(z)를 제거한다. 이 때의 세정액으로서는 시판의 것 등을 사용할 수 있다. 시판품으로서는 EKC Technology Inc. 제작의 EKC 265(등록상표), Ashland Chemical 제작의 ACT935(등록상표), Mitsubishi Gas Chemical 제작의 ELM C-30(상품명) 등이 열거된다. 이들의 제품에 관해서는 특허문헌으로도 공개되어 있다(미국특허 제5279771호 명세서, 미국특허 제5419779호 명세서, 미국특허 제5630904호 명세서 참조).Here, after the ashing for removing the photoresist film, the semiconductor substrate formed up to the opening portion H exposing the
본 실시형태에 있어서는 상기 세정 공정 후에 상술한 산화방지액을 적용하는 린스 공정을 갖는다(공정 (g) 참조). 이 때의 린스조건은 이미 설명한 바와 같다. 본 실시형태에 의하면, 상술한 산화방지액의 작용이 발휘되고 패드 표면에서 노출된 알루미늄-구리 합금(Al-Cu)막(52)의 표면이 처리되어 거기에 부동태막(p)이 형성된다. 도시된 것은 모식화하여 나타낸 것이고, 두께가 있는 막(층)으로서 인식할 수 있는 것이 아니어도 좋다. 이와 같이, 산화방지액에 의해 Al-Cu막(52) 표면이 보호되어 산화방지성이 부여되었기 때문에, 그 후에 계속되는 다이싱 공정에 있어서 대량의 물 또는 수성매체에 노출되어도 Al-Cu막의 부식(침식)이 억제·방지된다. 따라서, 본 실시형태에 의하면, 이 패드에 본딩 와이어 등을 접속시켰을 때에 피팅 부식 등이 없는 양호한 전기적 특성이 발휘된다. 그것에 의해 높은 수율을 실현할 수 있다.In this embodiment, it has a rinse process which applies the antioxidant liquid mentioned above after the said washing process (refer process (g)). The rinse condition at this time is as described above. According to the present embodiment, the action of the above-described antioxidant solution is exerted, and the surface of the aluminum-copper alloy (Al-Cu)
(실시예)(Example)
이하, 실시예에 의해 본 발명을 더욱 상세하게 설명한다. 단, 본 발명은 이들 실시예에 의해 한정되지 않는다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, this invention is not limited by these Examples.
(실시예 I)(Example I)
<실시예, 비교예, 참고예><Example, Comparative Example, Reference Example>
이하의 표 1에 나타낸 성분을 거기에 나타낸 조성(질량%)으로 물에 함유시켜 산화방지액을 조액했다(실시예·비교예). 물은 반도체 제조 공정에 사용되는 일반적인 초순수를 사용했다. 표 중에 조성(질량%)을 나타낸 성분은 이 양으로 함유되고, 염기성 화합물은 각 시료에 대해서 나타낸 pH가 되는 양으로 함유되었다. 이들은 물의 조성(질량%)을 합쳐서 100질량%가 되는 것을 의미한다. 표 중의 pH는 실온(20℃)에 있어서 HORIBA 제작의 F-51(상품명)로 측정한 값이다. 또한, 비교예 1은 인산을 포함하지 않는 약액에서의 린스 실험을 나타낸 것이다.The components shown in Table 1 below were contained in water in the composition (mass%) shown therein to prepare an antioxidant solution (Examples and Comparative Examples). Water used general ultrapure water used in semiconductor manufacturing processes. The component which showed the composition (mass%) in the table was contained in this quantity, and the basic compound was contained in the quantity which becomes the pH shown about each sample. These mean that the composition (mass%) of water adds up to 100 mass%. PH in a table | surface is the value measured with F-51 (brand name) by HORIBA make at room temperature (20 degreeC). In addition, Comparative Example 1 shows a rinse experiment in a chemical solution containing no phosphoric acid.
잔사의 제거에는 Mitsubishi Gas Chemical 제작의 ELM C-30(상품명)의 잔사 제거액을 사용하고 20℃에서 매옆식 제거장치(SPS-EuropeB.V. 제작, POLOS(등록상표))를 사용하여 행했다.To remove the residue, a residue removal liquid of ELM C-30 (trade name) manufactured by Mitsubishi Gas Chemical was used, and a lateral type removal apparatus (manufactured by SPS-Europe B.V., POLOS (registered trademark)) was used at 20 ° C.
상기 잔사의 세정 후, 각각 조제한 산화방지액을 도 1d의 공정(e)에 나타낸 구조를 갖는 반도체 기판에 도포하여 린스 처리를 행했다. 반도체 기판의 금속막(52)에는 알루미늄-구리 합금(구리 0.5질량% 함유), 실리콘 산화막(3)에는 SiO2를 적용한 것을 사용했다. 각 실시예·비교예에 있어서 적용한 금속막의 재료 종류는 표 1에 나타냈다.After washing | cleaning the said residue, the antioxidant solution prepared respectively was apply | coated to the semiconductor substrate which has a structure shown to process (e) of FIG. 1D, and the rinse process was performed. An aluminum-copper alloy (containing 0.5% by mass of copper) was used for the
<다이싱 공정에 의한 부식(침식)><Corrosion (erosion) by dicing process>
우선, 상기 반도체 기판(집적회로 부착 웨이퍼)을 미리 환상 프레임에 고정된 UV(Ultra Violet) 테이프에 부착하고, 이어서, 고정된 반도체 기판을 유수에 노출시킨 후에 다이아몬드 쏘우(saw)를 사용하여 절단 라인을 따라 종, 횡으로 절단하여 반도체 기판을 개편화(個片化)했다(다이싱 공정). 또한, 개편화한 반도체 기판은 UV 테이프를 통하여 프레임에 고정되어 있기 때문에 정렬한 상태를 유지하고 있다. 그 후에, UV 테이프에 대하여 UV를 조사함으로써 점착력을 저하시키고 개편화한 반도체 기판이 박리되기 쉬워 그것을 UV 테이프로부터 픽업했다.First, the semiconductor substrate (wafer with integrated circuit) is attached to UV (Ultra Violet) tape fixed in advance to the annular frame, and then the fixed semiconductor substrate is exposed to flowing water, followed by cutting lines using a diamond saw. The semiconductor substrate was separated into pieces by cutting longitudinally and laterally (dicing step). Moreover, since the semiconductor substrate separated into pieces is being fixed to the frame via UV tape, it maintains the aligned state. Thereafter, by irradiating the UV tape with UV, the adhesive force was reduced and the semiconductor substrate separated into pieces easily peeled off, and it was picked up from the UV tape.
상기 공정을 통하여 얻어진 개편화한 반도체 기판을 부식성 평가에 제공했다. 개편화된 반도체 기판은 온도: 25℃, 습도: 50%의 환경하에서 30일간 정치되고, 그 후, 반도체 기판의 금속막(52) 표면(55)을 관찰함으로써 평가했다. 이 관찰에는 광학현미경을 사용하고 50배의 배율을 주된 조건으로서 행했다. 이 관찰에 의해 이하와 같이 구별하여 좋고 나쁨을 평가했다. 그 결과를 이하 표 1에 나타냈다.The separated semiconductor substrate obtained through the said process was used for corrosion evaluation. The separated semiconductor substrate was left to stand for 30 days in an environment of temperature: 25 ° C and humidity: 50%, and then evaluated by observing the
AA: 흑점의 수가 0개/㎛2 AA: Number of sunspots 0 / 탆 2
A: 흑점의 수가 1∼2개/㎛2 A: number of
B: 흑점의 수가 3∼9개/㎛2 B: number of sunspots 3-9 / 탆 2
C: 흑점의 수가 10개/㎛2 이상C: Number of
본 발명의 산화방지방법 및 산화방지액에 의하면(실시예), 이 처리를 행하지 않은 경우(비교예 1)와 비교하여 반도체 기판에 있어서의 금속막 표면의 산화에 의한 침식(피팅 부식)을 효과적으로 억제할 수 있었다. 또한, pH가 바람직한 범위로 조절되어 있으므로 금속막이나 절연층을 부식시키는 경우가 없고(실시예·참고예를 비교하여 참조), 또한 다이싱 공정에 있어서 다량으로 부여되는 물의 영향을 완화시켜 양호한 금속막 표면의 유지를 가능하게 하는 것을 알 수 있다.According to the antioxidant method and the antioxidant solution of the present invention (Example), as compared with the case where this treatment is not performed (Comparative Example 1), the erosion (fitting corrosion) due to oxidation of the metal film surface on the semiconductor substrate is effectively performed. Could be restrained. Moreover, since pH is adjusted to a preferable range, it does not corrode a metal film or an insulating layer (refer an Example and reference example), and also moderates the influence of the water provided in a large amount in a dicing process, and is favorable metal. It can be seen that it is possible to maintain the membrane surface.
또한, 상기 표 1에 있어서의 약호가 나타낸 화합물은 이하와 같다.In addition, the compound shown by the symbol in the said Table 1 is as follows.
(인 함유 화합물)(Phosphorus containing compound)
P1: 인산(Phosphoric acid)P1: Phosphoric acid
P2: 폴리 인산(Poly phosphoric acid)P2: Poly phosphoric acid
P3: 포스폰산(Phosphonic acid)P3: Phosphonic acid
P4: 5산화 2인(Phophorous pentoxide)P4: Phosphorous pentoxide
P5: 차아인산(Dihydridohydroxidooxidophosphorus)P5: Dihydridohydroxidooxidophosphorus
P6: 포스카르넷(Foscarnet)P6: Foscarnet
P7: 에틸포스폰산(Ethyl phosphonic acid)P7: ethyl phosphonic acid
P8: 1-히드록시에탄-1,1-비스(포스폰산)P8: 1-hydroxyethane-1,1-bis (phosphonic acid)
(1-Hydroxyethane-1,1-bis(phosphonic acid)) (1-Hydroxyethane-1,1-bis (phosphonic acid))
(유기 카르복실산 화합물)(Organic Carboxylic Acid Compound)
AA: 아세트산AA: acetic acid
BA: 벤조산BA: benzoic acid
CA: 시트르산CA: citric acid
DGA: 디글리콜산(옥시 2아세트산)DGA: diglycolic acid (oxy diacetic acid)
FRA: 포름산FRA: formic acid
GA: 글리콜산GA: glycolic acid
GLA: 글루콘산GLA: Gluconic Acid
LA: 락트산LA: lactic acid
MA: 말산MA: Malic acid
MLA: 말레산MLA: Maleic acid
MNA: 말론산MNA: malonic acid
OA: 옥살산OA: Oxalic Acid
PA: 프로피온산PA: propionic acid
PHA: 프탈산PHA: phthalic acid
PHHA: 프탈로히드록삼산PHHA: phthalohydroxamic acid
SA: 살리실산SA: salicylic acid
SHA: 살리실히드록삼산SHA: salicylic acid
SUA: 숙신산(호박산)SUA: Succinic acid
TA: 주석산TA: tartaric acid
(염기성 화합물)(Basic compound)
DEA: 디에탄올아민DEA: diethanolamine
DGAm: 디글리콜아민DGAm: Diglycolamine
BTMAH: 벤질트리메틸암모늄 히드록시드BTMAH: Benzyltrimethylammonium Hydroxide
KOH: 수산화 칼륨KOH: Potassium Hydroxide
MEA: 2-아미노에탄올MEA: 2-aminoethanol
TEA: 트리에탄올아민TEA: Triethanolamine
TMAH: 테트라메틸암모늄 히드록시드TMAH: Tetramethylammonium Hydroxide
TBAH: 테트라부틸암모늄 히드록시드TBAH: tetrabutylammonium hydroxide
(실시예 Ⅱ)(Example II)
또한, 실시예 I의 처리액을 사용하여 처리 시간에 대한 흑점의 수를 조사했다. 그 때, 기판을 전처리한 것과 하지 않은 것을 비교한 바, 전처리를 행한 것에서는 전처리를 하지 않은 것보다 빠르게 흑점의 수가 감소하는 것을 확인할 수 있었다. 전처리로서는 2.38% TMAH 수용액에 30초 침지한 후, 순수로 1분간 세정을 행했다.In addition, the number of sunspots with respect to processing time was investigated using the process liquid of Example I. At that time, it was confirmed that the number of sunspots decreased more quickly than the one without pretreatment when the substrate was pretreated and the one without pretreatment. As a pretreatment, after immersing in 2.38% TMAH aqueous solution for 30 second, it wash | cleaned for 1 minute with pure water.
(실시예 Ⅲ)(Example III)
이하의 표 2에 나타낸 성분을 거기에 나타낸 조성(질량%)으로 물에 함유시켜 산화방지액을 조액했다(실시예·비교예). 상세한 조제 조건은 실시예 I과 동일했다. 평가는 상술의 흑점 판정에 더해서 Orion Diagnostica Oy 제작의 상품명: 이지컬트(Easicult)(등록상표) M 및 이지컬트 TTC를 사용하고 25℃에서 5일간 배양하여 곰팡이·세균의 번식시험을 행했다. 결과를 하기와 같이 분류하여 표 2에 나타냈다.The components shown in Table 2 below were contained in water in the composition (mass%) shown therein to prepare an antioxidant solution (Examples and Comparative Examples). Detailed preparation conditions were the same as in Example I. The evaluation was carried out for 5 days at 25 ° C. using a brand name: Easicult (trademark) M and EasyCult TTC manufactured by Orion Diagnostica Oy, in addition to the above-described sunspot determination. The results were classified as follows and shown in Table 2.
3: 번식이 확인되지 않았다.3: Reproduction was not confirmed.
2: 103CFU/ml 이하로 번식이 확인되었다.2: Breeding was confirmed below 10 3 CFU / ml.
1: 103CFU/ml를 초과하는 번식이 확인되었다.1: Breeding above 10 3 CFU / ml was confirmed.
또한, 본 실시예에 있어서의 흑점의 판정시험에 있어서는 산화방지액 시료로서 곰팡이나 세균의 발생에 의해 영향받기 쉬워지는 7일간 대기 중에 실온(약 28℃)에서 보존한 후의 것을 사용했다.In addition, in the determination test of the sunspot in this Example, the thing after having stored at room temperature (about 28 degreeC) in air | atmosphere for 7 days which becomes easy to be influenced by the generation of mold and bacteria as an antioxidant liquid sample was used.
·인 함유 화합물, 염기성 유기 화합물, 카르복실산 화합물의 약칭은 상기 표 1의 주석 참조.For abbreviated names of phosphorus-containing compounds, basic organic compounds and carboxylic acid compounds, see the notes in Table 1 above.
(방미·방균제)(Flavor, Antibacterial)
EA: 2-메틸-4-이소티아졸린-3-온EA: 2-methyl-4-isothiazolin-3-one
EB: 1,2-벤조이소티아졸린-3-온EB: 1,2-benzoisothiazolin-3-one
EC: 5-클로로-2-메틸-4-이소티아졸린-3-온EC: 5-chloro-2-methyl-4-isothiazolin-3-one
ED: o-페닐페놀ED: o-phenylphenol
EE: p-클로로-m-크레졸EE: p-chloro-m-cresol
EF: 3-메틸-4-클로로페놀EF: 3-methyl-4-chlorophenol
EG: 소듐 2-피리딘티올-1-옥시드EG: sodium 2-pyridinethiol-1-oxide
EH: 헥사히드로-1,3,5-트리에틸-s-트리아진EH: hexahydro-1,3,5-triethyl-s-triazine
EI: 2,4,6-트리메틸피리디늄 p-톨루엔술포네이트EI: 2,4,6-trimethylpyridinium p-toluenesulfonate
EJ: 4-(2-니트로부틸)모르폴린EJ: 4- (2-nitrobutyl) morpholine
EK: 4,4'-(2-에틸-2-니트로트리메틸렌)디모르폴린EK: 4,4 '-(2-ethyl-2-nitrotrimethylene) dimorpholine
EL: 테트라메틸암모늄 클로라이드EL: tetramethylammonium chloride
EM: 도데실피리디늄 클로라이드EM: dodecylpyridinium chloride
상기의 결과로부터 알 수 있는 바와 같이, 본 발명의 바람직한 실시형태에 의하면, 곰팡이나 세균의 발생이 바람직하게 억제되어 소정 기간 대기 중에 보존한 후에도 높은 산화방지 효과가 얻어지는 것을 알 수 있다.As can be seen from the above results, according to a preferred embodiment of the present invention, it is understood that the generation of mold and bacteria is preferably suppressed and a high antioxidant effect can be obtained even after storage in the air for a predetermined period.
1, 2: 층간 절연층 3: 실리콘 산화막
4: 패시베이션막 5: 패드
51, 53: 밀착막 52: 알루미늄-구리 합금(Al-Cu)막
6: 비어 61: 바이메탈막
62: 텅스텐막 7, 8: 배선 패턴
H: 개구부 c: 피팅 부식(흑점)
p: 부동태막 z: 잔사1, 2: interlayer insulating layer 3: silicon oxide film
4: passivation film 5: pad
51, 53: adhesion film 52: aluminum-copper alloy (Al-Cu) film
6: beer 61: bimetal film
62:
H: opening c: fitting corrosion (black spot)
p: passivation z: residue
Claims (15)
상기 산화방지액으로서 물에 적어도 인 함유 화합물 및 염기성 화합물을 함유시켜 pH를 6∼10으로 조정한 것을 사용하는 것을 특징으로 하는 금속막 표면의 산화방지방법.In treating the surface of the metal film of the semiconductor substrate with an antioxidant solution,
A method for preventing oxidation of the surface of a metal film, characterized by using at least a phosphorus-containing compound and a basic compound in water and adjusting the pH to 6 to 10 as the antioxidant solution.
상기 산화방지액 중에 방미·방균제를 포함하는 것을 특징으로 하는 금속막 표면의 산화방지방법.The method of claim 1,
An anti-oxidation method on the surface of a metal film, characterized by containing an anti-bacterial and antibacterial agent in the antioxidant solution.
상기 방미·방균제는 페놀 구조, 피리딘 구조, 트리아진 구조, 모르폴린 구조, 이소티아졸린 구조, 피리디늄 구조, 4급 암모늄 구조 중 어느 하나를 포함하는 화합물인 것을 특징으로 하는 금속막 표면의 산화방지방법.The method of claim 2,
The anti-microbial and antimicrobial agent is a compound containing any one of a phenol structure, a pyridine structure, a triazine structure, a morpholine structure, an isothiazoline structure, a pyridinium structure, and a quaternary ammonium structure. Prevention method.
상기 인 함유 화합물은 무기 인 화합물 또는 유기 인 화합물인 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 1 or 2,
Said phosphorus containing compound is an inorganic phosphorus compound or an organic phosphorus compound, The antioxidant method of the metal film surface characterized by the above-mentioned.
상기 인 함유 화합물은 인산 화합물인 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 1 or 2,
The phosphorus containing compound is a phosphoric acid compound, characterized in that the oxidation method of the metal film surface.
상기 산화방지액에 유기 카르복실산 화합물을 더 함유시키는 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 1 or 2,
An organic carboxylic acid compound is further contained in the said antioxidant, The antioxidant method of the metal film surface characterized by the above-mentioned.
상기 염기성 화합물은 제4급 아민 화합물 또는 알카놀아민 화합물로 이루어지는 군으로부터 선택되는 하나 이상의 화합물인 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 1 or 2,
Wherein said basic compound is at least one compound selected from the group consisting of quaternary amine compounds or alkanolamine compounds.
상기 유기 카르복실산 화합물은 시트르산, 락트산, 아세트산, 프로피온산, 말산, 주석산, 말론산, 옥살산, 숙신산, 글루콘산, 글리콜산, 디글리콜산, 말레산, 벤조산, 프탈산, 살리실산, 살리실히드록삼산 및 프탈히드록삼산으로 이루어지는 군으로부터 선택되는 하나 이상의 화합물인 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 6,
The organic carboxylic acid compound is citric acid, lactic acid, acetic acid, propionic acid, malic acid, tartaric acid, malonic acid, oxalic acid, succinic acid, gluconic acid, glycolic acid, diglylic acid, maleic acid, benzoic acid, phthalic acid, salicylic acid, salicylic acid And at least one compound selected from the group consisting of phthalic hydroxamic acid.
상기 산화방지액에 의한 처리를 다이싱 공정 전에 실시하는 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 1 or 2,
The oxidation prevention method of the metal film surface characterized by performing the process by the said antioxidant liquid before a dicing process.
반도체 기판에 대하여 플라즈마 에칭을 행하는 에칭 공정 및/또는 반도체 기판 상의 레지스트에 대하여 애싱을 행하는 애싱 공정에 있어서, 상기 반도체 기판 상에 형성된 플라즈마 에칭 잔사 및/또는 애싱 잔사를 세정하는 세정 공정 후에 상기 산화방지액에 의한 처리를 실시하는 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 1 or 2,
In the etching step of performing plasma etching on the semiconductor substrate and / or the ashing step of ashing the resist on the semiconductor substrate, the oxidation prevention after the cleaning step of cleaning the plasma etching residue and / or ashing residue formed on the semiconductor substrate. The oxidation prevention method of the metal film surface characterized by performing the process by liquid.
상기 금속막은 알루미늄, 구리 및 알루미늄-구리 합금으로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 금속막 표면의 산화방지방법.The method according to claim 1 or 2,
And said metal film is selected from the group consisting of aluminum, copper and an aluminum-copper alloy.
물과 인 함유 화합물 및 염기성 화합물을 함유시켜 pH를 6∼10으로 조정하는 것을 특징으로 하는 산화방지액.As an antioxidant for treating the surface of a metal film of a semiconductor substrate:
An antioxidant solution containing water, a phosphorus containing compound and a basic compound to adjust the pH to 6 to 10.
방미·방균제를 더 포함하는 것을 특징으로 하는 산화방지액.The method of claim 12,
Antioxidant liquid further containing an antiseptic and antiseptic agent.
유기 카르복실산 화합물을 더 포함하는 것을 특징으로 하는 산화방지액.The method according to claim 12 or 13,
The antioxidant further contains an organic carboxylic acid compound.
pH를 6∼8로 한 것을 특징으로 하는 산화방지액.The method according to claim 12 or 13,
Antioxidant liquid whose pH was 6-8.
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