TWI471409B - Etching solution - Google Patents
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- TWI471409B TWI471409B TW99108179A TW99108179A TWI471409B TW I471409 B TWI471409 B TW I471409B TW 99108179 A TW99108179 A TW 99108179A TW 99108179 A TW99108179 A TW 99108179A TW I471409 B TWI471409 B TW I471409B
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
Description
本發明係有關用於半導體製程、液晶製程等之矽氧化膜之蝕刻液、其製造方法、使用該蝕刻液之蝕刻方法、及使用該蝕刻液之蝕刻處理物的製造方法。The present invention relates to an etching solution for a tantalum oxide film used in a semiconductor process, a liquid crystal process, or the like, a method for producing the same, an etching method using the etching solution, and a method for producing an etching solution using the etching solution.
矽氧化膜之濕蝕刻液係使用氫氟酸與氟化銨溶液的混合液之緩衝氫氟酸(例如，專利文獻1)。已知，在半導體製造步驟中，雖在置入了緩衝氫氟酸的藥液槽中浸漬晶圓來進行蝕刻，但通常藥液槽因晶圓浸漬而具有開口部，最後導致藥液成分的蒸發而使藥液組成經時地變化，對蝕刻率會有重大的影響。因此，隨著時間經過的同時，不得不使藥液全量交換，在處理的效率及資源的有效利用之點上因而發生了問題。The wet etching liquid of the tantalum oxide film is a buffered hydrofluoric acid using a mixture of hydrofluoric acid and an ammonium fluoride solution (for example, Patent Document 1). It is known that in the semiconductor manufacturing step, the wafer is immersed in a chemical solution tank in which hydrofluoric acid is buffered, and the chemical liquid tank has an opening portion due to wafer immersion, and finally the chemical liquid component is caused. Evaporation causes the composition of the chemical to change over time, which has a significant effect on the etching rate. Therefore, as time passes, the entire amount of the chemical liquid has to be exchanged, and thus problems occur in the efficiency of the treatment and the effective use of resources.
專利文獻1之段落編號[0005]中，係記載著「當藥液組成為HF：0.1%、NH4 F：40%之緩衝氫氟酸(BHF)時，熱氧化膜之蝕刻率在25℃時為1.6nm/min。但是若將如此之藥液置於濕度40%、空間環境溫度25℃的環境下3日，蝕刻率為4.2nm/min約增加至2.6倍。在如此之環境下變化的藥液，要於往後的半導體製程中使用是不可能的」。In paragraph number [0005] of Patent Document 1, it is described that "when the chemical composition is HF: 0.1%, NH 4 F: 40% buffered hydrofluoric acid (BHF), the etching rate of the thermal oxide film is 25 ° C. The time is 1.6 nm/min. However, if such a chemical solution is placed in an environment having a humidity of 40% and a space ambient temperature of 25 ° C for 3 days, the etching rate is increased to about 2.6 times at 4.2 nm/min. It is impossible to use the liquid medicine in the semiconductor process in the future."
緩衝氫氟酸中的氟化銨、銨離子及氫氟酸的解離係以下述(1)式～(4)式所示。The dissociation of ammonium fluoride, ammonium ion, and hydrofluoric acid in the buffered hydrofluoric acid is represented by the following formulas (1) to (4).
【化1】【化1】
NH4 F→NH4 + +F- (1)NH 4 F→NH 4 + +F - (1)
NH4 + NH3 +H+ (pKa=9.24) (2)NH 4 + NH 3 +H + (pKa=9.24) (2)
HFH+ +F- (pKa=3.17) (3)HF H + +F - (pKa=3.17) (3)
HF+F- HF2 - (4)HF+F - HF 2 - (4)
如專利文獻1所述之藥液組成(HF=0.1質量%、NH4 F=40質量%)之緩衝氫氟酸，若置於例如濕度40%、溫度25℃之環境下，則根據(2)式氨會蒸發，且會於液中產生質子(H+ )。因氫氟酸為pKa=3.17之弱酸，因此若產生H+ ，會與(1)式生成之氟化物離子(F- )反應而依(3)式產生氟化氫(HF)。生成之HF進一步與F- 反應而產生矽氧化膜之蝕刻種HF2 - 。因此，若放置如此之藥液組成的緩衝氟化氫酸不管，則藥液組成會變化而加速矽氧化膜之蝕刻率，而藥液會變得無法使用。The buffered hydrofluoric acid having the chemical composition (HF = 0.1% by mass, NH 4 F = 40% by mass) as described in Patent Document 1 is placed in an environment of, for example, a humidity of 40% and a temperature of 25 ° C, according to (2) The ammonia will evaporate and will produce protons (H + ) in the liquid. Since hydrofluoric acid is a weak acid having a pKa of 3.17, when H + is generated, it reacts with a fluoride ion (F - ) formed by the formula (1) to generate hydrogen fluoride (HF) according to the formula (3). Further generation of HF and F - etching species generated by reaction of HF silicon oxide film 2 -. Therefore, if a buffered hydrogen fluoride having such a chemical liquid is placed, the composition of the chemical liquid changes to accelerate the etching rate of the tantalum oxide film, and the chemical liquid becomes unusable.
又，在專利文獻1之段落編號[0019]中，係記載著「NH4 F濃度若超過30質量%，則藥液的蒸發量雖少，但藥液的組成比例會變化。因此，難以回復到原來之組成」。Further, in paragraph number [0019] of Patent Document 1, it is described that "if the NH 4 F concentration exceeds 30% by mass, the evaporation amount of the chemical liquid is small, but the composition ratio of the chemical liquid changes. Therefore, it is difficult to recover. To the original composition."
又，專利文獻1中，係記載了緩衝氫氟酸特別是關於HF濃度為0.1質量%以下NH4 F濃度為30質量%以下之緩衝氫氟酸，為使藥液組成之經時變化變小，在將組成調整用藥液供給至藥液槽後，使經組成變化之藥液槽中的藥液維持在所規定的藥液組成之技術。這不過是記載以控制藥液的使用環境而使藥液組成變化消失，並非是藉由藥液本身的改良而減少組成變化者。In addition, in the case of the buffered hydrofluoric acid, the buffered hydrofluoric acid having an HF concentration of 0.1% by mass or less and an NH 4 F concentration of 30% by mass or less is used to reduce the composition of the chemical composition over time. After the composition adjusting chemical solution is supplied to the chemical liquid tank, the chemical liquid in the chemical liquid tank having the composition change is maintained in a predetermined chemical liquid composition. This is merely to describe that the change in the composition of the chemical solution is lost by controlling the use environment of the chemical solution, and it is not the case that the composition change is reduced by the improvement of the chemical solution itself.
又已知，半導體製造步驟中，通常雖在置入了緩衝氫氟酸的藥液槽中浸漬晶圓來進行蝕刻，但因一般藥液槽會因晶圓浸漬而具有開口部的緣故，由前段的超純水潤洗槽會將水帶進藥液槽中而稀釋藥液成分，而導致藥液組成經時性的變化，對蝕刻率會有重大的影響。因此，隨著時間經過的同時，不得不使藥液全量交換，在處理的效率及資源的有效利用之點上因而發生了問題。Further, in the semiconductor manufacturing step, it is generally known that a wafer is immersed in a chemical solution tank in which hydrofluoric acid is buffered, and the etching is performed because the general chemical liquid tank has an opening due to wafer immersion. The ultra-pure water rinse tank in the previous stage will bring water into the liquid tank to dilute the liquid composition, which will cause a change in the composition of the liquid over time, which will have a significant impact on the etching rate. Therefore, as time passes, the entire amount of the chemical liquid has to be exchanged, and thus problems occur in the efficiency of the treatment and the effective use of resources.
[專利文獻1]特開平9-22891號公報[Patent Document 1] Japanese Patent Publication No. 9-22891
本發明係以提供一種最後伴隨藥液的蒸發等之組成變化少、藥液的交換頻率少，且可經時性地蝕刻矽氧化膜之蝕刻液為其目的。The present invention has an object of providing an etching solution in which the composition of the ruthenium oxide film is etched with a small amount of change in composition, such as evaporation of the chemical liquid, and the frequency of exchange of the chemical liquid is small.
本發明者們為了解決上述的課題而一再專致於研究的結果，得到下述的見解。The present inventors have repeatedly focused on the results of the research in order to solve the above problems, and have obtained the following findings.
若添加具有pKa較氫氟酸(pKa=3.17)高之酸與具有pKa較氨(pKa=9.24)高之鹼基的鹽(A‧B)至緩衝氫氟酸，可得以HF濃度與氧化膜蝕刻率之關係式(y=aX+b；y為氧化膜蝕刻率(/分)、X為氫氟酸濃度(質量%))下之斜率a小的蝕刻液。若為斜率a小的蝕刻液，則即使藥液蒸發而HF濃度變高，氧化膜蝕刻率的增加會更少。又，即使以水稀釋使HF濃度變低，氧化膜蝕刻率的減少會變少。If a salt having a higher pKa than hydrofluoric acid (pKa=3.17) and a salt having a higher pKa than the base of ammonia (pKa=9.24) are added to the buffered hydrofluoric acid, the HF concentration and the oxide film can be obtained. The relationship of the etching rate (y=aX+b; y is the oxide film etching rate ( /min), X is an etchant having a small slope a under hydrofluoric acid concentration (% by mass). When the etching liquid having a small slope a is used, even if the chemical liquid evaporates and the HF concentration becomes high, the increase in the etching rate of the oxide film is less. Further, even if the HF concentration is lowered by dilution with water, the decrease in the etching rate of the oxide film is reduced.
因此，即使放置緩衝氫氟酸，因伴隨藥液的蒸發等之組成變化小的緣故，並不會加速矽氧化膜之蝕刻率，其結果，可提供一藥液交換頻度少且壽命長的蝕刻液。而根據該見解進一步反覆研究的結果，遂完成本發明。Therefore, even if the buffered hydrofluoric acid is placed, the composition change due to evaporation of the chemical solution or the like is small, the etching rate of the tantalum oxide film is not accelerated, and as a result, etching with a small frequency of chemical exchange and long life can be provided. liquid. Based on the results of the above research, the present invention was completed.
意即，本發明係提供下述的蝕刻液。That is, the present invention provides the following etching liquid.
項1.一種蝕刻液，其係含有Item 1. An etching solution containing
(A)氫氟酸、(A) hydrofluoric acid,
(B)氟化銨、(B) ammonium fluoride,
(C)由具有pKa較氫氟酸(pKa=3.17)之pKa大的酸(C1)與具有pKa較氨(pKa=9.24)之pKa大的鹼(C2)所成的鹽、及(C) a salt formed from an acid (C1) having a pKa larger than that of hydrofluoric acid (pKa = 3.17) and a base (C2) having a pKa larger than that of ammonia (pKa = 9.24), and
(D)水。(D) Water.
項2.如項1所記載之蝕刻液，其中，酸(C1)之pKa係大於3.17，且小於7。Item 2. The etching solution according to Item 1, wherein the acid (C1) has a pKa of more than 3.17 and less than 7.
項3.如項1或2所記載之蝕刻液，其中，酸(C1)係由甲酸(pKa=3.75)、乙酸(pKa=4.56)、丙二酸(第2段pKa=5.28)、檸檬酸(第3段pKa=5.69)、順丁烯二酸(第2段pKa=5.83)、2-(N-嗎啉代基)乙磺酸(pKa=6.1)及碳酸(第1段pKa=6.35)所成之群選出的至少1種。Item 3. The etching solution according to Item 1 or 2, wherein the acid (C1) is derived from formic acid (pKa = 3.75), acetic acid (pKa = 4.56), malonic acid (second stage pKa = 5.28), citric acid (3rd stage pKa=5.69), maleic acid (2nd stage pKa=5.83), 2-(N-morpholino)ethanesulfonic acid (pKa=6.1) and carbonic acid (1st stage pKa=6.35) At least one of the selected groups.
項4.如項1～3中任一項所記載之蝕刻液，其中，酸(C1)係乙酸。The etching liquid according to any one of items 1 to 3, wherein the acid (C1) is acetic acid.
項5.如項1～4中任一項所記載之蝕刻液，其中，鹼(C2)係由第一級胺(C2a)、第二級胺(C2b)、第三級胺(C2c)及第四級銨(C2d)所成之群選出的至少1種。The etching solution according to any one of items 1 to 4, wherein the base (C2) is a primary amine (C2a), a second amine (C2b), a tertiary amine (C2c), and At least one selected from the group consisting of the fourth-order ammonium (C2d).
項6.如項5所記載之蝕刻液，其中，第一級胺(C2a)係由甲基胺(pKa=10.6)、乙基胺(pKa=10.6)、丙基胺(pKa=10.6)、丁基胺(pKa=10.6)、戊基胺(pKa=10.0)、乙醇胺(pKa=9.3)、丙醇胺(pKa=9.3)、丁醇胺(pKa=9.3)、甲氧基乙基胺(pKa=10.0)及甲氧基丙基胺(pKa=10.0)所成之群選出的至少1種。The etching solution according to Item 5, wherein the first-stage amine (C2a) is composed of methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), Butylamine (pKa = 10.6), amylamine (pKa = 10.0), ethanolamine (pKa = 9.3), propanolamine (pKa = 9.3), butanolamine (pKa = 9.3), methoxyethylamine ( At least one selected from the group consisting of pKa = 10.0) and methoxypropylamine (pKa = 10.0).
項7.如項5或6所記載之蝕刻液，其中，第二級胺(C2b)係由二甲基胺(pKa=10.8)、二乙基胺(pKa=10.9)及二丙基胺(pKa=10.8)所成之群選出的至少1種。Item 7. The etching solution according to Item 5 or 6, wherein the second-stage amine (C2b) is derived from dimethylamine (pKa = 10.8), diethylamine (pKa = 10.9), and dipropylamine ( pKa = 10.8) at least one selected from the group formed.
項8.如項5～7中任一項所記載之蝕刻液，其中，第三級胺(C2c)係由三甲基胺(pKa=9.80)及三乙基胺(pKa=10.72)所成之群選出的至少1種。The etching solution according to any one of items 5 to 7, wherein the tertiary amine (C2c) is formed from trimethylamine (pKa = 9.80) and triethylamine (pKa = 10.72). At least one selected from the group.
項9.如項5～8中任一項所記載之蝕刻液，其中，第四級銨(C2d)係由氫氧化四甲基銨(pKa=14.0)、氫氧化四乙基銨(pKa=14.0)及膽鹼(pKa=13.2)所成之群選出的至少1種。The etching solution according to any one of items 5-8, wherein the fourth-order ammonium (C2d) is tetramethylammonium hydroxide (pKa=14.0) and tetraethylammonium hydroxide (pKa= At least one selected from the group consisting of 14.0) and choline (pKa = 13.2).
項10.如項1～5中任一項所記載之蝕刻液，其中，鹼(C2)係氫氧化四甲基銨。The etching solution according to any one of items 1 to 5, wherein the base (C2) is tetramethylammonium hydroxide.
項11.如項1～10中任一項所記載之蝕刻液，其係進一步含有界面活性劑(E)。The etching liquid according to any one of items 1 to 10, further comprising a surfactant (E).
項12.一種項1～11中任一項所記載之蝕刻液的製造方法，其係將(A)～(D)予以混合，The method for producing an etching solution according to any one of items 1 to 11, wherein (A) to (D) are mixed.
(A)氫氟酸、(A) hydrofluoric acid,
(B)氟化銨、(B) ammonium fluoride,
(C)由具有pKa較氫氟酸(pKa=3.17)之pKa大的酸(C1)與具有pKa較氨(pKa=9.24)之pKa大的鹼(C2)所成的鹽、及(C) a salt formed from an acid (C1) having a pKa larger than that of hydrofluoric acid (pKa = 3.17) and a base (C2) having a pKa larger than that of ammonia (pKa = 9.24), and
(D)水。(D) Water.
項13.一種蝕刻方法，其係使用項1～11中任一項所記載之蝕刻液蝕刻處理被蝕刻物之蝕刻方法。Item 13. An etching method for etching an object to be etched by using an etching solution according to any one of Items 1 to 11.
項14.一種蝕刻處理物的製造方法，其係使用項1～11中任一項所記載之蝕刻液蝕刻處理被蝕刻物之蝕刻處理物的製造方法。Item 14. A method for producing an etched material, which is a method for producing an etched material for etching an object to be etched by using the etching solution according to any one of Items 1 to 11.
本發明之蝕刻液，係最後伴隨藥液的蒸發、稀釋等之組成變化少、藥液的交換頻率少，且可經時性地蝕刻矽氧化膜。In the etching liquid of the present invention, the composition change with the evaporation and dilution of the chemical liquid is small, the exchange frequency of the chemical liquid is small, and the tantalum oxide film can be etched over time.
本發明之蝕刻液係含有(A)氫氟酸、(B)氟化銨、(C)由具有pKa較氫氟酸(pKa=3.17)之pKa大的酸(C1)與具有pKa較氨(pKa=9.24)之pKa大的鹼(C2)所成的鹽及(D)水之緩衝氫氟酸。The etching solution of the present invention contains (A) hydrofluoric acid, (B) ammonium fluoride, (C) an acid (C1) having a pKa larger than pFO than hydrofluoric acid (pKa = 3.17) and having a pKa more than ammonia ( pKa = 9.24) a salt of a base having a large pKa (C2) and (D) a buffered hydrofluoric acid of water.
氫氟酸(A)的添加量，並無特別限定，但以添加適合實施蝕刻之氫氟酸(HF)濃度為佳。例如，對蝕刻液之總重量而言，以HF之濃度為10質量%以下，較佳為0.001～9質量%，更佳為0.005～8質量%，特別佳為0.005～7質量%之方式搭配即可。The amount of the hydrofluoric acid (A) to be added is not particularly limited, but it is preferred to add a hydrofluoric acid (HF) concentration suitable for etching. For example, the total weight of the etching solution is such that the concentration of HF is 10% by mass or less, preferably 0.001 to 9% by mass, more preferably 0.005 to 8% by mass, particularly preferably 0.005 to 7% by mass. Just fine.
氫氟酸之濃度若為此範圍，雖適合作為蝕刻液，但藥液中的HF濃度愈低，長時間放置後的蝕刻率變化(增加)會變大。本發明中，即使是該低HF濃度之蝕刻液，亦可藉由後述所規定之鹽的添加，而抑制蝕刻率的變化。When the concentration of hydrofluoric acid is in this range, it is suitable as an etching liquid, but the lower the HF concentration in the chemical liquid, the larger the etching rate (increased) after standing for a long time. In the present invention, even in the etching liquid having a low HF concentration, the change in the etching rate can be suppressed by the addition of the salt specified later.
氟化銨(NH4 F)(B)的含量為1～45質量%，較佳可為10～40質量%之任意濃度。The content of ammonium fluoride (NH 4 F) (B) is from 1 to 45% by mass, preferably from 10 to 40% by mass.
蝕刻液中所添加之鹽(C)係選自具有pKa較氫氟酸(pKa=3.17)之pKa大的酸(C1)與具有pKa較氨(pKa=9.24)之pKa大的鹼(C2)所成之鹽。若將該鹽添加於緩衝氫氟酸，可得以HF濃度與氧化膜蝕刻率之關係式(y=aX+b；y為氧化膜蝕刻率(/分)、X為氫氟酸濃度(質量%))下之斜率a小的蝕刻液。若為斜率a小的蝕刻液，即使藥液蒸發而HF濃度變高，氧化膜蝕刻率的增加會更少。又，即使以水稀釋使HF濃度變低，氧化膜蝕刻率的減少會變少。藉此，可得經時性蝕刻率變化少的蝕刻液。The salt (C) added to the etching solution is selected from an acid (C1) having a pKa larger than that of hydrofluoric acid (pKa = 3.17) and a base (C2) having a pKa larger than that of ammonia (pKa = 9.24). The salt made. If the salt is added to the buffered hydrofluoric acid, the relationship between the HF concentration and the oxide film etching rate can be obtained (y=aX+b; y is the oxide film etching rate ( /min), X is an etchant having a small slope a under hydrofluoric acid concentration (% by mass). If the etching liquid having a small slope a is used, even if the chemical liquid evaporates and the HF concentration becomes high, the increase in the etching rate of the oxide film is less. Further, even if the HF concentration is lowered by dilution with water, the decrease in the etching rate of the oxide film is reduced. Thereby, an etching liquid having a small change in the etch rate over time can be obtained.
鹽(C)中所用的酸(C1)方面，重要的是其pKa要大於3.17(氫氟酸之pKa)。因使用pKa大於氫氟酸(pKa=3.7)之酸(C1)，係可抑制上述(3)式所致之HF的產生。此結果係，即使經長時間放置，亦可抑制藥液組成之變化。In terms of the acid (C1) used in the salt (C), it is important that its pKa is greater than 3.17 (pKa of hydrofluoric acid). The use of the acid (C1) having a pKa greater than that of hydrofluoric acid (pKa = 3.7) suppresses the generation of HF due to the above formula (3). As a result, even if it is left for a long time, the change in the composition of the chemical solution can be suppressed.
此酸(C1)的具體例方面，可舉例如甲酸(pKa=3.75)、乙酸(pKa=4.56)、丙二酸(第2段pKa=5.28)、檸檬酸(第3段pKa=5.69)、順丁烯二酸(第2段pKa=5.83)、2-(N-嗎啉代基)乙磺酸(pKa=6.1)、碳酸(第1段pKa=6.35)等。此等之酸(C1)係可單獨使用1種，亦可組合2種以上使用之。酸(C1)方面，較佳為pKa大於3.17且小於7，更佳為pKa為4以上且小於7，再更佳為pKa4.5～6.5者。pKa在最佳範圍內之酸(C1)的具體例係乙酸(pKa=4.56)、丙二酸(第2段pKa=5.28)、檸檬酸(第3段pKa=5.69)、順丁烯二酸(第2段pKa=5.83)、2-(N-嗎啉代基)乙磺酸(pKa=6.1)、碳酸(第1段pKa=6.35)等，其中，係以乙酸(pKa=4.56)為佳。Specific examples of the acid (C1) include formic acid (pKa = 3.75), acetic acid (pKa = 4.56), malonic acid (pK = 5.28 in the second stage), and citric acid (pKa = 5.69 in the third stage). Maleic acid (pKa = 5.83 in the second stage), 2-(N-morpholino)ethanesulfonic acid (pKa = 6.1), carbonic acid (pKa = 6.35 in the first stage), and the like. These acids (C1) may be used alone or in combination of two or more. The acid (C1) preferably has a pKa of more than 3.17 and less than 7, more preferably a pKa of 4 or more and less than 7, and still more preferably a pKa of 4.5 to 6.5. Specific examples of the acid (C1) having an optimum pKa in the range are acetic acid (pKa = 4.56), malonic acid (pKa = 5.28 in the second stage), citric acid (pKa = 5.69 in the third stage), maleic acid. (PhD=5.83 in the second stage), 2-(N-morpholino)ethanesulfonic acid (pKa=6.1), carbonic acid (pKa=6.35 in the first stage), etc., wherein acetic acid (pKa=4.56) is used. good.
鹽(C)中所用的鹼(C2)方面，重要的是其pKa大於9.24(氨之pKa)。因使用pKa較氨(pKa=9.24)大的鹼(C2)，而可抑制上述(2)式所致之質子的產生。此結果係，即使經長時間放置，亦可抑制藥液組成之變化。In terms of the base (C2) used in the salt (C), it is important that its pKa is greater than 9.24 (pKa of ammonia). The use of the base (C2) having a larger pKa than ammonia (pKa = 9.24) suppresses the generation of protons due to the above formula (2). As a result, even if it is left for a long time, the change in the composition of the chemical solution can be suppressed.
此鹼(C2)方面，可使用有機胺類(例如第一級胺(C2a)、第二級胺(C2b)、第三級胺(C2c)、第四級銨(C2d)等)等。As the base (C2), an organic amine (for example, a first-grade amine (C2a), a second-grade amine (C2b), a tertiary amine (C2c), a fourth-order ammonium (C2d), or the like) can be used.
第一級胺(C2a)方面，可舉例如甲基胺(pKa=10.6)、乙基胺(pKa=10.6)、丙基胺(pKa=10.6)、丁基胺(pKa=10.6)、戊基胺(pKa=10.0)、乙醇胺(pKa=9.3)、丙醇胺(pKa=9.3)、丁醇胺(pKa=9.3)、甲氧基乙基胺(pKa=10.0)、甲氧基丙基胺(pKa=10.0)等；第二級胺(C2b)方面，可舉例如二甲基胺(pKa=10.8)、二乙基胺(pKa=10.9)、二丙基胺(pKa=10.8)等；第三級胺(C2c)方面，可舉例如三甲基胺(pKa=9.80)、三乙基胺(pKa=10.72)等；第四級銨方面，可舉例如氫氧化四甲基銨(pKa=14.0)、氫氧化四乙基銨(pKa=14.0)、膽鹼(pKa=13.2)等。此等之鹼(C2)係可單獨使用1種，亦可組合2種以上使用之。Examples of the first-order amine (C2a) include methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), butylamine (pKa = 10.6), and pentyl group. Amine (pKa = 10.0), ethanolamine (pKa = 9.3), propanolamine (pKa = 9.3), butanolamine (pKa = 9.3), methoxyethylamine (pKa = 10.0), methoxypropylamine (pKa = 10.0) and the like; and the second-stage amine (C2b) may, for example, be dimethylamine (pKa = 10.8), diethylamine (pKa = 10.9), dipropylamine (pKa = 10.8) or the like; The third-stage amine (C2c) may, for example, be trimethylamine (pKa = 9.80) or triethylamine (pKa = 10.72); and the fourth-order ammonium may, for example, be tetramethylammonium hydroxide (pKa). =14.0), tetraethylammonium hydroxide (pKa=14.0), choline (pKa=13.2), and the like. These bases (C2) may be used alone or in combination of two or more.
鹼(C2)方面，pKa係大於9.24者，較佳係pKa為10以上，更佳係pKa為10.5以上者。鹼(C2)之pKa的上限值雖無特別限制，但通常為14左右。In the case of the base (C2), the pKa system is more than 9.24, preferably a pKa of 10 or more, and more preferably a pKa of 10.5 or more. The upper limit of the pKa of the base (C2) is not particularly limited, but is usually about 14.
pKa在最佳範圍內之鹼(C2)的具體例係甲基胺(pKa=10.6)、乙基胺(pKa=10.6)、丙基胺(pKa=10.6)、丁基胺(pKa=10.6)、二甲基胺(pKa=10.8)、二乙基胺(pKa=10.9)、二丙基胺(pKa=10.8)、三乙基胺(pKa=10.72)、氫氧化四甲基銨(pKa=14.0)、氫氧化四乙基銨(pKa=14.0)、膽鹼(pKa=13.2)等，其中，以氫氧化四甲基銨為佳。Specific examples of the base (C2) in which the pKa is in the optimum range are methylamine (pKa = 10.6), ethylamine (pKa = 10.6), propylamine (pKa = 10.6), and butylamine (pKa = 10.6). , dimethylamine (pKa = 10.8), diethylamine (pKa = 10.9), dipropylamine (pKa = 10.8), triethylamine (pKa = 10.72), tetramethylammonium hydroxide (pKa = 14.0), tetraethylammonium hydroxide (pKa = 14.0), choline (pKa = 13.2), etc., of which tetramethylammonium hydroxide is preferred.
由上述酸(C1)與鹼(C2)所成較佳之鹽(C)的具體例方面，可舉出例如，由乙酸與甲基胺所成之鹽、由乙酸與乙基胺所成之鹽、由乙酸與二甲基胺所成之鹽、由乙酸與三甲基胺所成之鹽、由乙酸與氫氧化四甲基銨所成之鹽、由乙酸與膽鹼所成之鹽、由甲酸與氫氧化四甲基銨所成之鹽等。較佳為，由乙酸與氫氧化四甲基銨所成之鹽。Specific examples of the salt (C) which is preferably a compound (C1) and a base (C2) include a salt of acetic acid and methylamine, and a salt of acetic acid and ethylamine. a salt formed from acetic acid and dimethylamine, a salt formed from acetic acid and trimethylamine, a salt formed from acetic acid and tetramethylammonium hydroxide, a salt formed from acetic acid and choline, a salt of formic acid and tetramethylammonium hydroxide. Preferably, it is a salt of acetic acid and tetramethylammonium hydroxide.
鹽(C)的添加量，例如，對蝕刻液之總重量而言為0.01～5mol/kg，較佳為0.05～4mol/kg，更佳為0.1～3mol/kg。藉由使其為該範圍，即使在長時間放置後仍可獲得蝕刻率變化少的蝕刻液。The amount of the salt (C) to be added is, for example, 0.01 to 5 mol/kg, preferably 0.05 to 4 mol/kg, more preferably 0.1 to 3 mol/kg, based on the total weight of the etching liquid. By making it into this range, an etchant having a small change in etching rate can be obtained even after standing for a long period of time.
本發明之較佳的蝕刻液方面，係以蝕刻液的總重量為基準，可舉出含有氫氟酸(A)0.05～7質量%、氟化銨(B)1～45質量%、pKa為4.5～6.5之酸(C1)與pKa為10.5以上之鹼(C2)所成之鹽(C)0.1～3mol/kg及剩餘為水之矽氧化膜之蝕刻液。The preferred etching liquid of the present invention is based on the total weight of the etching solution, and includes hydrofluoric acid (A) in an amount of 0.05 to 7 mass%, ammonium fluoride (B) in an amount of 1 to 45 mass%, and pKa. An acid (C1) of 4.5 to 6.5 and a salt (C) of a base (C2) having a pKa of 10.5 or more (C) of 0.1 to 3 mol/kg and an etching solution of a remaining ruthenium oxide film of water.
本發明之蝕刻液中，可進一步添加界面活性劑(E)。界面活性劑(E)可對疏水性表面(Si表面、Poly-Si表面、光阻表面等)增加潤濕性，且依圖型的形狀可用以防止藥液不奏效之情況。其種類如陽離子系界面活性劑(E1)、陰離子系界面活性劑(E2)、非離子系界面活性劑(E3)等，並無特別限定。陽離子系界面活性劑(E1)方面可舉例如C8 H17 NH2 等之胺類，陰離子系界面活性劑(E2)方面可舉例如C8 H17 COOH等之烴系羧酸、C8 H17 SO3 H等之烴系磺酸、H(CF2 )6 COOH等之氟系羧酸等，非離子系界面活性劑(E3)方面可舉例如聚氧烯基烷基醚等之醚類等。In the etching solution of the present invention, a surfactant (E) can be further added. The surfactant (E) can increase the wettability on the hydrophobic surface (Si surface, Poly-Si surface, photoresist surface, etc.), and the shape according to the pattern can be used to prevent the liquid medicine from being ineffective. The type thereof is not particularly limited as long as it is a cationic surfactant (E1), an anionic surfactant (E2), or a nonionic surfactant (E3). Examples of the cationic surfactant (E1) include amines such as C 8 H 17 NH 2 , and examples of the anionic surfactant (E2) include hydrocarbon carboxylic acids such as C 8 H 17 COOH and C 8 H. 17 a hydrocarbon-based sulfonic acid such as SO 3 H or a fluorine-based carboxylic acid such as H(CF 2 ) 6 COOH, and the like. The nonionic surfactant (E3) may, for example, be an ether such as a polyoxyalkylene alkyl ether. Wait.
界面活性劑(E)的添加量(濃度)，雖無特別限定，但對蝕刻液之總重量而言為2000質量ppm以下，較佳為10～1500質量ppm，更佳為50～1200質量ppm。The amount (concentration) of the surfactant (E) is not particularly limited, but is 2,000 ppm by mass or less, preferably 10 to 1,500 ppm by mass, and more preferably 50 to 1200 ppm by mass based on the total weight of the etching solution. .
本發明之蝕刻液係可藉由混合氫氟酸(A)、氟化銨(B)、由具有pKa較氫氟酸(pKa=3.17)之pKa大的酸(C1)與具有pKa較氨(pKa=9.24)之pKa大的鹼(C2)所成的鹽(C)及水(D)而製造。端視其需要，亦可混合前述界面活性劑(E)。此外，混合方法並無特別限定，可採用公知之方法。The etching solution of the present invention can be obtained by mixing hydrofluoric acid (A), ammonium fluoride (B), an acid (C1) having a pKa larger than pFO than hydrofluoric acid (pKa = 3.17), and having a pKa ratio of ammonia ( It is produced by a salt (C) obtained by a base (C2) having a large pKa of pKa = 9.24) and water (D). The aforementioned surfactant (E) may also be mixed depending on its needs. Further, the mixing method is not particularly limited, and a known method can be employed.
對含有本發明之蝕刻液的矽氧化膜之晶圓的適用上，矽氧化膜若為可蝕刻去除者，並無特別限定，可例示塗佈、浸漬、噴霧、噴射等之任意方法。特別是利用經時性的組成變化少且蝕刻率變化少之優點，係以將晶圓浸漬於蝕刻液之方法(批次式裝置)，以及朝晶圓噴射蝕刻液之方法(群集式裝置)為佳。In the application of the wafer containing the tantalum oxide film of the etching liquid of the present invention, the tantalum oxide film is not particularly limited as long as it can be etched and removed, and any method such as coating, dipping, spraying, and spraying can be exemplified. In particular, the method of immersing a wafer in an etching liquid (batch type device) and spraying an etching liquid toward a wafer (cluster type device) is advantageous in that the change in composition with little change over time is small and the change in etching rate is small. It is better.
本發明之蝕刻液的適用溫度為15～90℃左右，較佳為室溫附近，因此左右之溫度下蝕刻液適用於晶圓之故，係可適用於蝕刻矽氧化膜。蝕刻液的適用時間雖視矽氧化膜之膜厚等而定，但一般為5秒～30分鐘。The etching temperature of the etching solution of the present invention is about 15 to 90 ° C, preferably about room temperature. Therefore, the etching liquid is suitable for use in a wafer at a temperature of left and right, and is suitable for etching a tantalum oxide film. The application time of the etching solution depends on the film thickness of the ruthenium oxide film, etc., but it is usually 5 seconds to 30 minutes.
以本發明之蝕刻液處理所得之蝕刻處理物，係可以超純水等進行潤洗。The etching treatment obtained by treating the etching solution of the present invention can be rinsed with ultrapure water or the like.
[實施例][Examples]
以下顯示實施例，以使本發明之特徵更為明確。但本發明並不受限於此等實施例。The embodiments are shown below to make the features of the present invention clearer. However, the invention is not limited to the embodiments.
實施例1～3及比較例1：蒸發試驗Examples 1-3 and Comparative Example 1: Evaporation test
使50質量%之氫氟酸(A)、40質量%之氟化銨(B)(含HF0.07質量%)、表1所示之酸與鹼所成之鹽(C)、及水(D)以所規定之濃度混合來調製蝕刻液400g。HF濃度係以50質量%之氫氟酸(A)來補足所添加氟化銨(B)中含有之氫氟酸量的不足部分而調整。又，鹽(C)之調製所使用的酸及鹼係使用：乙酸為100質量%濃度者、CH3 CH2 NH2 為70質量%水溶液、(CH3 )3 NOH為25質量%水溶液。50% by mass of hydrofluoric acid (A), 40% by mass of ammonium fluoride (B) (containing HF of 0.07% by mass), a salt (C) of an acid and an alkali shown in Table 1, and water ( D) 400 g of an etching liquid was prepared by mixing at a predetermined concentration. The HF concentration is adjusted by supplementing the insufficient portion of the amount of hydrofluoric acid contained in the added ammonium fluoride (B) with 50% by mass of hydrofluoric acid (A). Further, the acid and the base used for the preparation of the salt (C) are used in an amount of 100% by mass of acetic acid, 70% by mass of an aqueous solution of CH 3 CH 2 NH 2 , and an aqueous solution of 25% by mass of (CH 3 ) 3 NOH.
[蝕刻液之重量測定][Measurement of the weight of the etching solution]
將經調製之蝕刻液的半份保存於密閉的容器中。剩餘的半份置入直徑8cm的圓筒容器中，測定容器內的液重(初期重量)。之後，於通風設備內依所規定的時間實施放置試驗。進行所規定的時間放置試驗後，再度測定容器內的重量(放置後重量)。進行放置試驗時，使通風設備內之溫度為18～22℃、濕度為25～35%。A half of the prepared etching solution was stored in a closed container. The remaining half was placed in a cylindrical container having a diameter of 8 cm, and the liquid weight (initial weight) in the container was measured. Thereafter, the placement test was carried out in the ventilation equipment at the prescribed time. After the prescribed time placement test, the weight inside the container (weight after placement) was measured again. When the placement test is carried out, the temperature in the ventilation device is 18 to 22 ° C and the humidity is 25 to 35%.
[蝕刻率之測定方法][Method for measuring etching rate]
將保存於密閉容器之蝕刻液與在通風設備進行放置試驗之蝕刻液移至於其他個別的容器中，且於恒溫槽調整液溫至25℃。蝕刻率之測定係以膜厚約1000之1.5cm×1.2cm的熱氧化膜片(薄膜)來實施。The etchant stored in the closed container and the etchant placed in the ventilating device were transferred to other individual containers, and the temperature was adjusted to 25 ° C in a constant temperature bath. The etching rate is determined by a film thickness of about 1000. The 1.5 cm x 1.2 cm thermal oxide film (film) was used.
測定初期膜厚之後，將個別的熱氧化膜片在一定時間(2.5分、5分、10分)浸漬於藥液中，之後，以水潤洗藥液，以氮氣使其乾燥後，測定各膜片之膜厚。令浸漬前後的膜厚差為蝕刻量，且使縱軸為蝕刻量、橫軸為蝕刻時間時，其斜率為蝕刻率。又，令保存於密閉容器中之液的蝕刻率為初期熱氧化膜蝕刻率(初期ER)，且令用於放置試驗之液的蝕刻率為放置後熱氧化膜之蝕刻率(放置後ER)。After the initial film thickness was measured, the individual thermal oxide sheets were immersed in the chemical solution for a predetermined period of time (2.5 minutes, 5 minutes, and 10 minutes), and then the solution was rinsed with water, dried with nitrogen, and then each was measured. The film thickness of the diaphragm. When the film thickness difference before and after immersion is the etching amount, and the vertical axis is the etching amount and the horizontal axis is the etching time, the slope is the etching rate. Further, the etching rate of the liquid stored in the sealed container is the initial thermal oxide film etching rate (initial ER), and the etching rate of the liquid used for the placement test is the etching rate of the thermal oxide film after standing (ER after leaving). .
膜厚之測定係使用NanoSpec 3000AF-T(NANOMETRICS JAPAN(股)製)。For the measurement of the film thickness, NanoSpec 3000AF-T (manufactured by NANOMETRICS JAPAN Co., Ltd.) was used.
又，蝕刻率(ER)增加倍率係以下述之式進行計算。Further, the increase rate of the etching rate (ER) is calculated by the following formula.
ER增加倍率=[放置後熱氧化膜蝕刻率(放置後ER)]/[初期熱氧化膜蝕刻率(初期ER)]ER increase magnification = [thermal oxide film etching rate after placement (ER after placement)] / [initial thermal oxide film etching rate (initial ER)]
實施例1～3及比較例1之組成係如表1所示，其結果顯示於表2。The compositions of Examples 1 to 3 and Comparative Example 1 are shown in Table 1, and the results are shown in Table 2.
通風設備內藥液放置所致之蝕刻率增加倍率，係因添加由乙酸與乙基胺所成之鹽、由乙酸與氫氧化四甲基銨所成之鹽，而可較無添加者來得低。The increase rate of the etching rate caused by the placement of the liquid in the ventilation device is due to the addition of a salt formed from acetic acid and ethylamine, a salt formed from acetic acid and tetramethylammonium hydroxide, which is lower than that of no added person. .
實施例4～5及參考例1：蒸發試驗Examples 4 to 5 and Reference Example 1: Evaporation test
調整蝕刻液中的NH4 F濃度使其為2質量%，且除了使NH4 F濃度、鹽(C)之種類、鹽(C)的添加量如表3所示進行調整之外，其餘係與實施例1～3及比較例1同樣地，調製實施例4～5及參考例1之蝕刻液。此外，乙酸及CH3 CH2 NH2 係使用與實施例1～3及比較例1相同者，而膽鹼則使用44質量%水溶液。The concentration of NH 4 F in the etching solution was adjusted to 2% by mass, and the addition amount of the NH 4 F concentration, the salt (C) type, and the salt (C) was adjusted as shown in Table 3, and the others were The etching liquids of Examples 4 to 5 and Reference Example 1 were prepared in the same manner as in Examples 1 to 3 and Comparative Example 1. Further, acetic acid and CH 3 CH 2 NH 2 were used in the same manner as in Examples 1 to 3 and Comparative Example 1, and choline was used in a 44% by mass aqueous solution.
實施例4～5及參考例1的組成如表3所示，其結果顯示於表4。The compositions of Examples 4 to 5 and Reference Example 1 are shown in Table 3, and the results are shown in Table 4.
令NH4 F濃度為2質量%時，因添加由乙酸與氫氧化四甲基銨所成之鹽、由乙酸與膽鹼所成之鹽，而相較於無添加者，係可減低蝕刻率增加倍率，可得與實施例1～3及比較例1同樣的結果。When the NH 4 F concentration is 2% by mass, a salt formed from acetic acid and tetramethylammonium hydroxide and a salt formed from acetic acid and choline are added, and the etching rate can be reduced as compared with no addition. When the magnification was increased, the same results as in Examples 1 to 3 and Comparative Example 1 were obtained.
實施例6～7及比較例2：水稀釋試驗Examples 6-7 and Comparative Example 2: Water dilution test
藉由與藥液蒸發試驗中所示之同樣的藥液調合法調合各藥液1000g，且以表5所示規定的量與水混合調製藥液200g，測定25℃中之蝕刻率。Each of the chemical solutions was mixed with 1000 g of the same chemical liquid as shown in the chemical vapor evaporation test, and 200 g of the chemical solution was mixed with water in an amount specified in Table 5, and the etching rate at 25 ° C was measured.
[蝕刻率之測定方法][Method for measuring etching rate]
將保存於密閉容器中之蝕刻液的溫度以恒溫槽調整至25℃，其中將1.5cm×1.2cm之熱氧化膜片(薄膜)在初期膜厚測定後浸漬於各藥液中5分鐘，之後，以水潤洗藥液且以氮氣使其乾燥後，測定各膜片之膜厚。使浸漬前後的膜厚差作為蝕刻量，且使蝕刻量除以蝕刻時間作為蝕刻率。The temperature of the etching solution stored in the sealed container was adjusted to 25 ° C in a constant temperature bath, and a 1.5 cm × 1.2 cm thermal oxide film (film) was immersed in each liquid solution for 5 minutes after the initial film thickness measurement, and then After washing with a hydrating solution and drying with nitrogen, the film thickness of each film was measured. The difference in film thickness before and after the immersion was used as the etching amount, and the etching amount was divided by the etching time as the etching rate.
將實施例6～7及比較例2之組成顯示於表5，其結果顯示於表6。The compositions of Examples 6 to 7 and Comparative Example 2 are shown in Table 5, and the results are shown in Table 6.
在添加有0.5mol/kg由乙酸與四甲基氫氧化物所成之鹽的緩衝氫氟酸(實施例6)，相較於未添加鹽者(比較例2)，其蝕刻率的變動少。又，添加有1mol/kg由乙酸與四甲基氫氧化物所成之鹽的緩衝氫氟酸(實施例7)，即使以水稀釋，幾乎沒有蝕刻率的變動，且與實施例6比較，仍可抑制蝕刻率之變動。The buffered hydrofluoric acid (Example 6) to which 0.5 mol/kg of a salt derived from acetic acid and tetramethyl hydroxide was added was less in change in etching rate than in the case where no salt was added (Comparative Example 2). . Further, buffered hydrofluoric acid (Example 7) containing 1 mol/kg of a salt of acetic acid and tetramethyl hydroxide was added, and even if diluted with water, there was almost no variation in etching rate, and compared with Example 6, The variation in the etching rate can still be suppressed.
實施例8～11及比較例3～4：添加之鹽的種類‧添加量與熱氧化膜蝕刻率之關係Examples 8 to 11 and Comparative Examples 3 to 4: Types of Salts Added ‧ Addition Amount and Thermal Oxide Film Etching Rate
將50質量%之氫氟酸(A)、40質量%之氟化銨(B)(含有HF0.07質量%)、如表7所示之酸與鹼所成之鹽(C)、及水(D)以所規定之濃度混合調製蝕刻液200g。HF濃度係以改變50質量%之氫氟酸的添加量為0.25質量%、0.5質量%、0.75質量%或1質量%進行調製。此外，因40質量%之氟化銨中原本就含有0.07質量%之氫氟酸，故又加入此量調整HF濃度。又，使用乙酸為100質量%者，CH3 CH2 NH2 係70質量%水溶液、(CH3 )4 NOH係25質量%水溶液50% by mass of hydrofluoric acid (A), 40% by mass of ammonium fluoride (B) (containing HF 0.07% by mass), a salt (C) of an acid and a base as shown in Table 7, and water (D) 200 g of an etching liquid was mixed and prepared at a predetermined concentration. The HF concentration is adjusted by adding 50% by mass of hydrofluoric acid in an amount of 0.25% by mass, 0.5% by mass, 0.75% by mass or 1% by mass. Further, since 40% by mass of ammonium fluoride originally contained 0.07% by mass of hydrofluoric acid, this amount was added to adjust the HF concentration. Further, when acetic acid is used as 100% by mass, CH 3 CH 2 NH 2 is 70% by mass aqueous solution, and (CH 3 ) 4 NOH is 25% by mass aqueous solution.
[蝕刻率之測定方法][Method for measuring etching rate]
將1.5cm×1.2cm之熱氧化膜片(薄膜)於初期膜厚測定後浸漬於各藥液5分鐘，之後，以水潤洗藥液，且以氮氣使其乾燥後，測定各膜片之膜厚。使浸漬前後的膜厚差作為蝕刻量，且使蝕刻量除以蝕刻時間作為蝕刻率。A 1.5 cm × 1.2 cm thermal oxide film (film) was immersed in each chemical solution for 5 minutes after the initial film thickness measurement, and then the drug solution was rinsed with water and dried with nitrogen gas, and then each film was measured. Film thickness. The difference in film thickness before and after the immersion was used as the etching amount, and the etching amount was divided by the etching time as the etching rate.
將實施例8～11及比較例3～4之NH4 F濃度、鹽的種類及鹽的添加量顯示於表7，且將HF濃度及結果顯示於表8。此外，y=ax+b關係式中的a及b係藉由測定3種類之HF濃度中的蝕刻率，且由其結果以最小平方法來算出(3點測定)。The NH 4 F concentration, the type of the salt, and the amount of the salt added in Examples 8 to 11 and Comparative Examples 3 to 4 are shown in Table 7, and the HF concentration and the results are shown in Table 8. Further, a and b in the relationship of y=ax+b are measured by the etching rate in the three types of HF concentrations, and the results are calculated by the least square method (three-point measurement).
就實施例8～11及比較例3～4之結果，將HF濃度為橫軸、蝕刻率為縱軸所成的曲線圖形顯示於圖1。The results of Examples 8 to 11 and Comparative Examples 3 to 4 are shown in Fig. 1 as a graph in which the HF concentration is on the horizontal axis and the etching rate is on the vertical axis.
如比較例3(鹽無添加)、實施例10(添加0.5mol/kg(CH3 COOH+(CH3 )4 NOH)者)及實施例11(添加1mol/kg(CH3 COOH+(CH3 )4 NOH)者)所示，鹽的添加濃度愈高，蝕刻率的斜率就愈小。For example, Comparative Example 3 (salt no addition), Example 10 (addition of 0.5 mol/kg (CH 3 COOH + (CH 3 ) 4 NOH)) and Example 11 (addition of 1 mol/kg (CH 3 COOH + (CH 3 ) 4 ) As shown by NOH), the higher the concentration of the salt added, the smaller the slope of the etching rate.
比較先前所示蒸發試驗之比較例1(無添加鹽，對應至比較例3)、實施例1(添加1mol/kg(CH3 COOH+CH3 CH2 NH2 )者，對應至實施例8)、實施例2(添加0.5mol/kg(CH3 COOH+(CH3 )4 NOH)者，對應至實施例10)、及實施例3(添加1mol/kg(CH3 COOH+(CH3 )4 NOH)者，對應至實施例11)之蝕刻率增加倍率與圖1所示之蝕刻率的斜率，並將結果顯示於表9。Comparative Example 1 (no added salt, corresponding to Comparative Example 3) and Example 1 (addition of 1 mol/kg (CH 3 COOH + CH 3 CH 2 NH 2 ), corresponding to Example 8) were compared with the evaporation test shown previously. Example 2 (addition of 0.5 mol/kg (CH 3 COOH + (CH 3 ) 4 NOH), corresponding to Example 10), and Example 3 (addition of 1 mol/kg (CH 3 COOH + (CH 3 ) 4 NOH) The etch rate increase magnification of Example 11) and the slope of the etch rate shown in Fig. 1 were shown, and the results are shown in Table 9.
由表9可知，蝕刻率的斜率愈小，蒸發試驗所致之蝕刻率的增加倍率就愈小。As can be seen from Table 9, the smaller the slope of the etching rate, the smaller the increase rate of the etching rate due to the evaporation test.
又，比較先前所示水稀釋試驗的比較例2(無添加鹽者，對應至比較例3)、實施例6(添加0.5mol/kg(CH3 COOH+(CH3 )4 NOH)者，對應至實施例10)及實施例7(添加1mol/kg(CH3 COOH+(CH3 )4 NOH)者，對應至實施例11)之初期之蝕刻率(未稀釋時)與以緩衝氫氟酸：水=90：10稀釋時的蝕刻率之比(ER降低倍率；以緩衝氫氟酸：水=90：10稀釋時之ER/初期之ER)與圖1所示之蝕刻率的斜率，並將其結果顯示於表10。Further, comparing Comparative Example 2 (corresponding to Comparative Example 3) and Example 6 (adding 0.5 mol/kg (CH 3 COOH + (CH 3 ) 4 NOH)) in the water dilution test shown previously, the corresponding Example 10) and Example 7 (addition of 1 mol/kg (CH 3 COOH + (CH 3 ) 4 NOH), corresponding to the initial etching rate of Example 11) (undiluted) and buffered hydrofluoric acid: water =90:10 ratio of etching rate at the time of dilution (ER reduction magnification; ER/initial ER when buffered with hydrofluoric acid:water=90:10) and the slope of the etching rate shown in Fig. 1 and The results are shown in Table 10.
由表10可知，蝕刻率的斜率愈小，水稀釋試驗所致之蝕刻率的降低倍率就愈少。As can be seen from Table 10, the smaller the slope of the etching rate, the less the reduction ratio of the etching rate due to the water dilution test.
如此，藉由調查由HF濃度與熱氧化膜蝕刻量所求得之斜率，係可預測伴隨藥液蒸發或稀釋所致之蝕刻量的變動大小。Thus, by investigating the slope obtained from the HF concentration and the amount of etching of the thermal oxide film, it is possible to predict the variation in the amount of etching caused by evaporation or dilution of the chemical solution.
實施例12～21及比較例5～11：添加之鹽的種類‧濃度與熱氧化膜蝕刻率之關係2Examples 12 to 21 and Comparative Examples 5 to 11: Types of added salts ‧ Relationship between concentration and thermal oxide film etching rate 2
與實施例8～11及比較例3～4同樣地調製蝕刻液，且以與實施例8～11及比較例3～4同樣的方法測定蝕刻率。The etching liquid was prepared in the same manner as in Examples 8 to 11 and Comparative Examples 3 to 4, and the etching rate was measured in the same manner as in Examples 8 to 11 and Comparative Examples 3 to 4.
將實施例12～21及比較例5～11之NH4 F濃度、鹽的種類、鹽的添加量、界面活性劑的種類及界面活性劑的添加量顯示於表11，且將HF濃度及結果顯示於表12。此外，在此亦與實施例8～11及比較例3～4同樣地，y=ax+b關係式中的a及b係藉由測定3種類之HF濃度中的蝕刻率，且由其結果以最小平方法來算出(3點測定)。The NH 4 F concentration, the type of the salt, the amount of the salt added, the type of the surfactant, and the amount of the surfactant added in Examples 12 to 21 and Comparative Examples 5 to 11 are shown in Table 11, and the HF concentration and results were obtained. Shown in Table 12. Further, similarly to Examples 8 to 11 and Comparative Examples 3 to 4, a and b in the relationship of y=ax+b are measured by the etching rate in the three types of HF concentrations, and the results are obtained. Calculated by the least square method (3 points measurement).
由表12亦可知，與表10同樣地，蝕刻率的斜率愈小，水稀釋試驗所致之蝕刻率的降低倍率就愈少。As is clear from Table 12, as in Table 10, the smaller the slope of the etching rate, the smaller the reduction ratio of the etching rate due to the water dilution test.
[圖1]就實施例8～11及比較例3～4，顯示其HF濃度與蝕刻率之關係的曲線圖形。Fig. 1 is a graph showing the relationship between the HF concentration and the etching rate in Examples 8 to 11 and Comparative Examples 3 to 4.
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