TW202325827A

TW202325827A - Post etching residues cleaning solution with titanium nitride removal

Info

Publication number: TW202325827A
Application number: TW112101301A
Authority: TW
Inventors: 柯志正; 王哲偉; 喬恩尼司席爾多瑞絲維李恩提納斯胡格布曼; 安卓亞斯克里普
Original assignee: 德商巴斯夫歐洲公司
Priority date: 2018-06-11
Filing date: 2018-06-11
Publication date: 2023-07-01

Abstract

The present invention relates to a composition capable of achieving high TiN etching and removal of organic polymers and residues without damaging Cu, Co and/or Ru or risking the damage of other materials present in the structure, e.g. low-k materials, said composition comprising: (a) an organic amine; (b) one or more inhibitor(s); (c) one or more buffer(s); (d) an activator; (e) one or more glycol ether(s); (f) optionally an aprotic solvent; and (g) water. The present invention also relates to a kit comprising said composition in combination with an oxidizer, and the use thereof.

Description

可移除氮化鈦的蝕刻後殘渣清理溶液Post etch residue cleaning solution to remove titanium nitride

本發明涉及用於半導體/IC生產領域中的注入後、蝕刻/蝕刻後和灰後相關處理的組成物。更具體地，本發明涉及一種組成物，該組成物對碳氟（CFx）聚合物和有機殘渣具有良好的清潔性能，能夠完全移除或縮減金屬硬掩模（例如氮化鈦（TiN）），同時保護作為互連的襯裡、帽或阻擋層的Cu、Co和Ru。The present invention relates to compositions for post-implantation, etch/post-etch and post-ash related processes in the field of semiconductor/IC production. More specifically, the present invention relates to a composition having good cleaning performance against fluorocarbon (CFx) polymers and organic residues, capable of completely removing or shrinking metal hard masks such as titanium nitride (TiN) , while protecting Cu, Co, and Ru as interconnect liners, caps, or barriers.

積體電路（IC）由矽襯底中或矽襯底上形成的數百萬有源器件組成。最初相互隔離的有源器件被結合在一起形成功能電路和元件。這些器件通過使用眾所周知的多層互連部進行互連。互連結構通常具有第一金屬化層、互連層、第二金屬化層級，並且近年來具有第三及以後的金屬化層級。An integrated circuit (IC) consists of millions of active devices formed in or on a silicon substrate. Active devices that were initially isolated from each other are combined to form functional circuits and components. These devices are interconnected using well-known multilayer interconnects. Interconnect structures typically have a first metallization level, an interconnect level, a second metallization level, and more recently third and subsequent metallization levels.

在半導體/IC生產領域中，通常通過濕法清理工藝移除蝕刻後殘渣（PER）。可以在這裡使用包含絡合劑和水的溶液。此外，在微電子結構內的不同層的選擇性刻蝕被認為是IC製造工藝中的關鍵和至關重要的步驟。In the field of semiconductor/IC production, post-etch residue (PER) is usually removed by a wet cleaning process. A solution comprising a complexing agent and water can be used here. Furthermore, selective etching of different layers within microelectronic structures is considered a critical and vital step in the IC fabrication process.

在第一層和後續的金屬化層中，期望具有高TiN蝕刻速率，並且為了實現高TiN蝕刻速率，需要高水準的氧化劑以實現高水準的TiN蝕刻。此外，用於多次構圖工藝的幹法蝕刻步驟會產生重碳氟（CFx）聚合物，這些聚合物非常難以從IC結構表面移除。因此，還需要使用氧化劑來分解CFx聚合物。在主要包含銅（Cu-塞）的後續金屬化層中，期望能夠以銅塞不被顯著損壞的速率蝕刻TiN。取決於TiN和金屬層各自的厚度（這在很大程度上取決於所使用的集成方案），需要能夠調整TiN和金屬的蝕刻速率的溶液。In the first and subsequent metallization layers, a high TiN etch rate is desired, and to achieve a high TiN etch rate, a high level of oxidizer is required to achieve a high level of TiN etch. Additionally, the dry etch step used in the multiple patterning process produces heavy fluorocarbon (CFx) polymers that are very difficult to remove from the surface of the IC structure. Therefore, it is also necessary to use an oxidizing agent to decompose the CFx polymer. In subsequent metallization layers comprising mainly copper (Cu-plugs), it is desirable to be able to etch the TiN at a rate at which the Cu-plugs are not significantly damaged. Depending on the respective thicknesses of the TiN and metal layers, which largely depends on the integration scheme used, a solution capable of tuning the etch rates of TiN and metal is required.

應該理解的是製劑中存在氧化劑（如過氧化氫）可能是實現足夠高的TiN蝕刻速率所必需的。然而，銅和相關金屬的蝕刻速率（例如Co，Cu和Ru腐蝕）通過添加如過氧化氫的氧化劑而增加是不希望的效果。因此，在一側上移除CFx聚合物而對TiN實現足夠高的蝕刻速率與在另一側上實現對金屬（例如Cu，Co和Ru）的足夠低的蝕刻速率之間必須進行微妙的平衡。為了實現這一點，其它組分被添加到溶液中，例如，腐蝕抑制劑、活化劑、緩衝劑組分和溶劑。It should be understood that the presence of an oxidizing agent such as hydrogen peroxide in the formulation may be necessary to achieve a sufficiently high TiN etch rate. However, the increase in etch rate of copper and related metals (e.g. Co, Cu and Ru corrosion) by addition of oxidizing agents like hydrogen peroxide is an undesired effect. Therefore, a delicate balance must be struck between achieving a sufficiently high etch rate for TiN while removing CFx polymer on one side and achieving a sufficiently low etch rate for metals such as Cu, Co, and Ru on the other side . To achieve this, other components are added to the solution, for example, corrosion inhibitors, activators, buffer components and solvents.

另一個問題是，當清理越來越多的晶片時，伴隨著TiN與氧化劑（如過氧化氫）的反應，由於形成酸性反應產物（例如，H2TiO3），溶液的pH下降，這導致TiN蝕刻速率下降。這個問題與組成物的回收能力有關，這在該領域非常重要且難以實現。Another problem is that when cleaning more and more wafers, along with the reaction of TiN with oxidizing agents such as hydrogen peroxide, the pH of the solution drops due to the formation of acidic reaction products (e.g., H2TiO3), which leads to a decrease in the TiN etch rate. decline. This problem is related to the recovery ability of the composition, which is very important and difficult to achieve in this field.

US7,919,445涉及一種用於移除蝕刻後殘渣的新穎溶液。優選地添加作為腐蝕抑制劑的咪唑啉化合物用於處理晶片表面。US 7,919,445 relates to a novel solution for removing post-etch residues. An imidazoline compound is preferably added as a corrosion inhibitor for treating the wafer surface.

WO03060045涉及用於從半導體襯底移除光致抗蝕劑、蝕刻和灰殘渣以及污染物的含水組成物。在剝離和清理組成物中可以使用單一的腐蝕抑制劑化合物或腐蝕抑制劑的混合物，例如苯並***、苯甲酸、丙二酸、沒食子酸、兒茶酚、丙二酸銨。WO03060045不使用氧化劑來蝕刻TiN，也沒有討論Cu、Co或Ru的保護。WO03060045 relates to aqueous compositions for removing photoresist, etch and ash residues and contaminants from semiconductor substrates. A single corrosion inhibitor compound or a mixture of corrosion inhibitors such as benzotriazole, benzoic acid, malonic acid, gallic acid, catechol, ammonium malonate may be used in the stripping and cleaning composition. WO03060045 does not use an oxidizing agent to etch TiN, nor does it discuss protection of Cu, Co or Ru.

WO06138505涉及緻密流體組成物，例如超臨界流體組成物，其用於從微電子器件的表面移除硬化的光致抗蝕劑、蝕刻後殘渣和/或底部抗反射塗層。然而，所述流體組成物中含有至少一種氟化物源，這將損害低k介電材料。WO06138505不涉及TiN的蝕刻以及Cu、Co或Ru的保護。WO06138505 relates to dense fluid compositions, such as supercritical fluid compositions, for the removal of hardened photoresist, post etch residue and/or bottom antireflective coatings from the surface of microelectronic devices. However, the fluid composition contains at least one source of fluoride, which will damage the low-k dielectric material. WO06138505 is not concerned with etching of TiN and protection of Cu, Co or Ru.

顯然，需要找到一種組成物，該組成物可以實現高TiN蝕刻並移除CFx聚合物而不損害Cu、Co或Ru，也沒有損害結構中存在的其它材料（如，低k材料）的風險。此外，還需要解決經常觀察到的由於反應產物積聚引起的晶片負載增加時TiN蝕刻速率的下降，從而回收組成物以繼續使用（再迴圈模式使用）。目標可以通過本申請的組成物來實現。Clearly, there is a need to find a composition that can achieve high TiN etch and remove CFx polymer without damaging Cu, Co or Ru, and without risking damage to other materials (eg, low-k materials) present in the structure. In addition, the frequently observed decrease in TiN etch rate with increased wafer loading due to reaction product buildup needs to be addressed to recycle the composition for continued use (recycling mode use). The object can be achieved by the composition of the present application.

因此，本發明提供一種可回收組成物，其能夠實現高TiN蝕刻和CFx聚合物的移除，而基本不蝕刻Cu、Co和Ru，或者不存在對結構中存在的其它材料（例如，低k材料）的損害的風險，所述組成物包括： a）有機胺； b）一種或多種抑制劑； c）一種或多種緩衝劑； d）活化劑； e）一種或多種乙二醇醚； f）任選的非質子溶劑； g）水。 Thus, the present invention provides a recyclable composition that enables high TiN etch and CFx polymer removal with substantially no etching of Cu, Co, and Ru, or no impact on other materials present in the structure (e.g., low-k material), the composition of which includes: a) Organic amines; b) one or more inhibitors; c) one or more buffers; d) activators; e) one or more glycol ethers; f) optional aprotic solvents; g) water.

本發明的另一方面是使用上述組成物與氧化劑組合來調節Cu/Co/Ru和TiN的蝕刻速率和/或移除有機和/或無機殘渣，該製劑包括： A）組成物，包括： a）有機胺； b）一種或多種抑制劑； c）一種或多種緩衝劑； d）活化劑； e）一種或多種乙二醇醚； f）任選的非質子溶劑； g）水； B）氧化劑，如過氧化氫、臭氧水、過硫酸。 Another aspect of the present invention is to use the above composition in combination with an oxidizing agent to adjust the etch rate of Cu/Co/Ru and TiN and/or remove organic and/or inorganic residues, the formulation comprising: A) Composition, including: a) Organic amines; b) one or more inhibitors; c) one or more buffers; d) activators; e) one or more glycol ethers; f) optional aprotic solvents; g) water; B) Oxidizing agent, such as hydrogen peroxide, ozone water, persulfuric acid.

結合附圖，根據下面的詳細描述，本發明的其它目的、優點和新穎特徵將變得更加明顯。Other objects, advantages and novel features of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.

儘管本公開容許各種形式的實施方式，但下文中將描述當前優選的實施例，但應理解的是，本公開應被認為是本公開的實例，並非旨在將本公開限制為所示的具體實施例。While the present disclosure is susceptible to various forms of embodiments, the presently preferred embodiments will be described below, with the understanding that this disclosure should be considered an example of this disclosure and is not intended to limit the disclosure to the specific ones shown. Example.

在本申請的一個實施例中，組成物通過混合以下來製備：a）有機胺；b）一種或多種抑制劑；c）一種或多種緩衝劑；d）活化劑；e）一種或多種乙二醇醚；f）任選的非質子溶劑；g）水。該組成物可用於製備在半導體/IC生產過程期間可調節TiN和Cu/Co/Ru蝕刻速率以及可移除聚合物（殘渣）的製劑。為此，可以將氧化劑添加到組成物中。In one embodiment of the present application, the composition is prepared by mixing: a) an organic amine; b) one or more inhibitors; c) one or more buffers; d) an activator; alcohol ether; f) optional aprotic solvent; g) water. The composition can be used to prepare formulations that can tune TiN and Cu/Co/Ru etch rates and remove polymers (residue) during semiconductor/IC manufacturing processes. For this purpose, an oxidizing agent can be added to the composition.

因此，在本申請的另一個實施例中，製劑通過以任何順序混合a）有機胺、b）一種或多種抑制劑、c）一種或多種緩衝劑、d）活化劑、e）一種或多種乙二醇醚、f）任選的非質子溶劑和g）水，然後加入氧化劑來製備。Thus, in another embodiment of the present application, the formulation is formulated by mixing in any order a) an organic amine, b) one or more inhibitors, c) one or more buffers, d) an activator, e) one or more B Glycol ethers, f) optional aprotic solvents and g) water, followed by addition of an oxidizing agent are prepared.

然後，將待處理的無圖案晶片（TiN，Cu/Co/Ru，低k）或圖案化晶片破碎成試樣，然後與製備的組成物接觸。Then, the unpatterned wafer (TiN, Cu/Co/Ru, low-k) or the patterned wafer to be processed was broken into samples, which were then contacted with the prepared composition.

如圖1到圖2所示，同時進行殘渣移除和TiN蝕刻，同時通過改變組成物中的組分來控制TiN與Cu/Co/Ru的蝕刻速率。此外，可以用適當的溶劑或溶劑混合物，例如水和/或異丙醇（IPA），通過沖洗移除表面上殘留的任何組分。As shown in Figures 1 to 2, residue removal and TiN etching are carried out at the same time, and the etching rates of TiN and Cu/Co/Ru are controlled by changing the components in the composition. In addition, any remaining components on the surface can be removed by rinsing with an appropriate solvent or solvent mixture, such as water and/or isopropanol (IPA).

有機胺與氧化劑結合可使聚合物更易溶于水。此外，有機胺可以穩定氧化劑，使得組成物的再迴圈和再利用成為可能。有機胺可以選自以下項：1-甲基咪唑；咪唑；吡唑；4-乙醯嗎啉；N-甲醯嗎啉；1,3,5-三(二甲基氨丙基)-均六氫三嗪；4-甲基吡啶N-氧化物；2-甲基吡啶N-氧化物；4-甲氧基吡啶N-氧化物水合物；4-氯吡啶N-氧化物；8-甲基喹啉N-氧化物；1-十二烷胺, N,N-二甲基-N-氧化物；4-甲基嗎啉4-氧化物；1-十四烷胺, N,N-二甲基-N-氧化物；(C ₁₀-C ₁₆)烷基二甲基胺氧化物；(C _12-18)烷基二甲基-N-氧化物；吡啶1-氧化物；癸胺, N,N-二甲基-N-氧化物；十六烷胺, N,N-二甲基-N-氧化物。優選地，有機胺可以選自4-甲基嗎啉4-氧化物和1,3,5-三(二甲基氨丙基)-均六氫三嗪。 Organic amines combined with oxidizing agents can make polymers more water soluble. In addition, organic amines can stabilize the oxidant, making recycling and reuse of the composition possible. The organic amine may be selected from the following: 1-methylimidazole; imidazole; pyrazole; 4-acetylmorpholine; N-formylmorpholine; Hexahydrotriazine; 4-methylpyridine N-oxide; 2-methylpyridine N-oxide; 4-methoxypyridine N-oxide hydrate; 4-chloropyridine N-oxide; 8-methylpyridine Quinoline N-oxide; 1-dodecylamine, N,N-dimethyl-N-oxide; 4-methylmorpholine 4-oxide; 1-tetradecylamine, N,N- Dimethyl-N-oxide; (C ₁₀ -C ₁₆ )alkyldimethylamine oxide; (C _12-18 )alkyldimethyl-N-oxide; pyridine 1-oxide; decylamine , N,N-Dimethyl-N-oxide; Hexadecylamine, N,N-Dimethyl-N-oxide. Preferably, the organic amine may be selected from 4-methylmorpholine 4-oxide and 1,3,5-tris(dimethylaminopropyl)-sexahydrotriazine.

以組成物的總重量計，存在于本發明的組成物中有機胺的量的範圍可以是從0.01到25 wt%，優選地從0.1到15 wt%。The amount of organic amine present in the composition of the invention may range from 0.01 to 25 wt%, preferably from 0.1 to 15 wt%, based on the total weight of the composition.

在優選實施例中，以組成物的總重量計，作為有機胺存在於組成物中的4-甲基嗎啉4-氧化物的量的範圍是從0.5到20 wt%，優選地為5到20 wt%，最優選地為8到15 wt%。例如，以組成物的總重量計，作為有機胺存在於組成物中的4-甲基嗎啉4-氧化物的量為8 wt%。In a preferred embodiment, the amount of 4-methylmorpholine 4-oxide present in the composition as an organic amine ranges from 0.5 to 20 wt%, preferably 5 to 20 wt%, based on the total weight of the composition. 20 wt%, most preferably 8 to 15 wt%. For example, the amount of 4-methylmorpholine 4-oxide present in the composition as an organic amine is 8 wt % based on the total weight of the composition.

該抑制劑是Cu、Co或Ru的腐蝕抑制劑，並且可以選自稱為聚乙烯亞胺（a類）、唑類（b類）及其衍生物的化合物類別。各種化合物的蝕刻速率可以通過改變各種類型的抑制劑中的官能團來控制。The inhibitor is a corrosion inhibitor of Cu, Co or Ru and may be selected from the classes of compounds known as polyethyleneimines (group a), azoles (group b) and their derivatives. The etch rate of various compounds can be controlled by changing the functional groups in various types of inhibitors.

（A）聚乙烯亞胺：BASF Lupasol® FG、G20、G35、G100、PR8515、HF、P、PS、PO100、PN 50、PN 60、SK；(A) Polyethyleneimine: BASF Lupasol® FG, G20, G35, G100, PR8515, HF, P, PS, PO100, PN 50, PN 60, SK;

（B）唑類：組氨酸，腺苷，腺嘌呤；吡啶；苯並異二唑；2,2'-聯吡啶；4,4'-雙(氯甲基)-2,2'-聯吡啶；1,2,3-***；1,2,4-***；四唑；五唑，1,3,4-噁二唑；噁二唑，1,2,3-噁二唑；1,2,5-噁二唑；1,2,4-噁二唑；噻唑；1,2,3-噻二唑；1,2,4-噻二唑；1,2,5-噻二唑；1,3,4-噻二唑；苯並***（BTA）；5-烷基苯並***（烷基=-C _nH _2n+1，其中n=1-6）；6-烷基苯並***（烷基=-C _nH _2n+1，其中n=1-6）；5-氨基-苯並***；6-氨基-苯並***；1-(甲氧基甲基)-1H-苯並***；1H-苯並***-1-甲醇；1-(氯甲基)-1H-苯並***；5-苯基-苯並***；N,N-雙(2-乙基己基)-4-甲基-1H-苯並***-1-甲胺；N,N-雙(2-乙基己基)-5-甲基-1H-苯並***-1-甲胺；2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇；5-硝基-苯並***；苯並***羧酸；1-氨基-1,2,4-***；羥基苯並***；2-(5-氨基-戊基)-苯並***；1-氨基-1,2,3-***；1-氨基-5-甲基-1,2,3-***；3-氨基-1,2,4-***；5-氨基-1,2,4-***；3-異丙基-1,2,4-***；3,5-二氨基-1,2,4-***；5-苯基硫醚苯並***；5-鹵基-苯並***（鹵基= F、Cl、Br或I）；6-鹵基-苯並***（鹵基= F、Cl、Br或I）；萘並***；4-甲基-2-苯基咪唑；5-氨基四唑；戊四唑；5-苯基-1H-四唑；5-苄基-1H-四唑；5-甲基四唑；2-苄基吡啶；2,4-二氨基-6-甲基-1,3,5-三嗪；甲基四唑；咪唑啉酮； (B) Azoles: histidine, adenosine, adenine; pyridine; benzisodiazole; 2,2'-bipyridine;4,4'-bis(chloromethyl)-2,2'-bisPyridine;1,2,3-triazole;1,2,4-triazole;tetrazole; pentazole, 1,3,4-oxadiazole; oxadiazole, 1,2,3-oxadiazole; 1,2,5-oxadiazole; 1,2,4-oxadiazole; thiazole; 1,2,3-thiadiazole; 1,2,4-thiadiazole; 1,2,5-thiadiazole azole; 1,3,4-thiadiazole; benzotriazole (BTA); 5-alkylbenzotriazole (alkyl=-C _n H _2n+1 , where n=1-6); 6- Alkylbenzotriazole (alkyl=-C _n H _2n+1 , where n=1-6); 5-amino-benzotriazole; 6-amino-benzotriazole; 1-(methoxy Methyl)-1H-benzotriazole; 1H-benzotriazole-1-methanol; 1-(chloromethyl)-1H-benzotriazole; 5-phenyl-benzotriazole; N,N -Bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine; N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole Azole-1-methylamine; 2,2'-[[(5-methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol;5-nitro-benzotriazole; Benzotriazole carboxylic acid; 1-amino-1,2,4-triazole; hydroxybenzotriazole; 2-(5-amino-pentyl)-benzotriazole; 1-amino-1,2, 3-triazole; 1-amino-5-methyl-1,2,3-triazole; 3-amino-1,2,4-triazole; 5-amino-1,2,4-triazole; 3 -Isopropyl-1,2,4-triazole; 3,5-Diamino-1,2,4-triazole; 5-phenylsulfidebenzotriazole; 5-halo-benzotriazole (halo = F, Cl, Br or I); 6-halo-benzotriazole (halo = F, Cl, Br or I); naphthotriazole; 4-methyl-2-phenylimidazole ;5-aminotetrazole; pentylenetetrazole; 5-phenyl-1H-tetrazole; 5-benzyl-1H-tetrazole; 5-methyltetrazole; -6-methyl-1,3,5-triazine; methyl tetrazole; imidazolinone;

1,5-戊四唑，咪唑啉硫酮；4-氨基-4H-1,2,4-***；苯並噻唑；苯並咪唑。1,5-Pentene tetrazole, imidazoline thione; 4-Amino-4H-1,2,4-triazole; Benzothiazole; Benzimidazole.

以組成物的總重量計，存在于本發明的組成物中的抑制劑的量的範圍可以是從0.01到6 wt%，優選地從0.5到2 wt%。The inhibitor may be present in the composition of the invention in an amount ranging from 0.01 to 6 wt%, preferably from 0.5 to 2 wt%, based on the total weight of the composition.

在優選實施例中，以組成物的總重量計，作為抑制劑存在於組成物中的BTA和6-甲基-苯並***的量的範圍分別是從0.1到6 wt%和0.01到5 wt%，優選0.5到3 wt%和0.1到2 wt%，最優選0.8到2 wt%和0.5到1 wt%。例如，以組成物的總重量計，作為抑制劑存在於組成物中的BTA和6-甲基-苯並***的量分別是1 wt%和1 wt%。In a preferred embodiment, the amount of BTA and 6-methyl-benzotriazole present in the composition as inhibitors ranges from 0.1 to 6 wt % and 0.01 to 5 wt %, respectively, based on the total weight of the composition. wt%, preferably 0.5 to 3 wt% and 0.1 to 2 wt%, most preferably 0.8 to 2 wt% and 0.5 to 1 wt%. For example, the amounts of BTA and 6-methyl-benzotriazole present in the composition as inhibitors are 1 wt% and 1 wt%, respectively, based on the total weight of the composition.

在化學方程1中給出了在存在過氧化氫時氧化和蝕刻TiN的可能反應方程之一。其中形成的H ₂TiO ₃是酸性的。而且，在該過程中，反應中形成的氨蒸發。這兩個過程都有助於穩定降低溶液的pH值，這會導致TiN和金屬的蝕刻速率發生變化。 (化學反應1) One of the possible reaction equations for oxidation and etching of TiN in the presence of hydrogen peroxide is given in Chemical Equation 1. The H ₂ TiO ₃ formed therein is acidic. Also, during this process, the ammonia formed in the reaction evaporates. Both processes contribute to a steady decrease in the pH of the solution, which causes changes in the etch rate of TiN and metal. (chemical reaction 1)

另外，根據化學方程式2和3，過氧化氫可以通過與Ti ⁴⁺離子反應而分解，釋放更多質子並進一步降低組成物的pH： (化學反應2) (化學反應3) Additionally, according to chemical equations 2 and 3, hydrogen peroxide can be decomposed by reacting with Ti ⁴⁺ ions, releasing more protons and further reducing the pH of the composition: (chemical reaction 2) (chemical reaction 3)

為了穩定TiN的蝕刻速率，必須補償酸積累和氨蒸發的這種影響，以確保組成物的pH穩定性。為此目的，可以將pH緩衝劑的概念應用於該機制，並且將緩衝劑體系加入到該組成物中。In order to stabilize the etch rate of TiN, such effects of acid accumulation and ammonia evaporation must be compensated to ensure the pH stability of the composition. For this purpose, the concept of pH buffers can be applied to this mechanism and a buffer system added to the composition.

緩衝液組分可以選自以下項：氫氧化銨；磷酸；四甲基氫氧化銨（TMAH）；四乙基氫氧化銨（TEAH）；四丁基氫氧化銨；甲醇胺（MEA）；乙醇胺（DEA）；三乙醇胺（TEA）；聚乙二醇胺；二甘醇胺；三甘醇胺；1,3,5-三(二甲氨基丙基)-均六氫三嗪。Buffer components may be selected from the following: ammonium hydroxide; phosphoric acid; tetramethylammonium hydroxide (TMAH); tetraethylammonium hydroxide (TEAH); tetrabutylammonium hydroxide; methanolamine (MEA); ethanolamine (DEA); Triethanolamine (TEA); Polyethylene glycol amine; Diethylene glycol amine; Triethylene glycol amine; 1,3,5-Tris(dimethylaminopropyl)-hexahydrotriazine.

以組成物的總重量計，存在于本發明的組成物中的緩衝劑的量的範圍可以是從0.01到5 wt%，優選地為0.5到2 wt%。Buffering agents may be present in the compositions of the invention in amounts ranging from 0.01 to 5 wt%, preferably 0.5 to 2 wt%, based on the total weight of the composition.

在優選實施例中，以組成物的總重量計，作為緩衝劑存在於組成物中的氫氧化銨和磷酸氫二銨的量的範圍分別是從0.01到1 wt%和0.01到5 wt%，優選的是從0.05到0.7 wt%和0.1到2 wt%，最優選的是從0.1到0.5 wt%和0.5到1.5 wt%。例如，以組成物的總重量計，作為緩衝劑存在於組成物中的氫氧化銨和磷酸氫二銨的量分別是0.12 wt%和1 wt%。In a preferred embodiment, the amount of ammonium hydroxide and diammonium phosphate present in the composition as a buffering agent ranges from 0.01 to 1 wt% and 0.01 to 5 wt%, respectively, based on the total weight of the composition, Preferred are from 0.05 to 0.7 wt% and 0.1 to 2 wt%, most preferred are from 0.1 to 0.5 wt% and 0.5 to 1.5 wt%. For example, the amounts of ammonium hydroxide and diammonium phosphate present in the composition as buffers are 0.12 wt% and 1 wt%, respectively, based on the total weight of the composition.

緩衝劑也可用於控制pH值，以防止一些敏感金屬（如高pH下的Co）腐蝕。本發明人發現，所要求保護的組成物在與過氧化氫混合時的pH值在6.0到7.5的窗口中，不僅降低了Cu、Co和Ru腐蝕，而且還有助於使對介電材料（低-k膜）的損害最小化。Buffers can also be used to control pH to prevent corrosion of some sensitive metals such as Co at high pH. The inventors have found that the claimed composition, in the pH window of 6.0 to 7.5 when mixed with hydrogen peroxide, not only reduces Cu, Co and Ru corrosion, but also contributes to the corrosion resistance of dielectric materials ( low-k film) damage is minimized.

但是，降低pH也會降低過氧化氫的氧化電位，導致TiN蝕刻速率不希望的下降。在該領域中，通常需要相對高濃度的氧化劑以實現足夠高的金屬硬掩模蝕刻速率。令人驚訝的是，發明人成功地發現了一系列活化劑以提高低pH狀態下的TiN蝕刻速率。因此，當向組成物中加入活化劑（如銨鹽和季銨鹽）以啟動TiN/氧化劑反應時，由此氧化劑的量減少，同時保持高TiN蝕刻速率。注意到一些活化劑也可以用作上述緩衝劑體系的組分。However, lowering the pH also lowers the oxidation potential of hydrogen peroxide, leading to an undesired decrease in the etch rate of TiN. In this field, relatively high concentrations of oxidizing agents are generally required to achieve sufficiently high metal hardmask etch rates. Surprisingly, the inventors succeeded in discovering a series of activators to increase the etch rate of TiN at low pH. Therefore, when activators such as ammonium salts and quaternary ammonium salts are added to the composition to initiate the TiN/oxidant reaction, thereby reducing the amount of oxidant while maintaining a high TiN etch rate. Note that some activators may also be used as components of the buffer system described above.

活化劑可以選自以下項：甲磺酸銨；磷酸二氫銨((NH ₄)H ₂PO ₄)；磷酸氫二銨（磷酸二銨，(NH ₄) ₂HPO ₄）；磷酸銨（(NH ₄) ₃PO ₄）；檸檬酸三銨；醋酸銨；乙二胺四乙酸銨；乙二胺四乙酸四銨；反式-1,2-亞環己基二次氮基四乙酸四銨；二亞乙基三胺五乙酸銨；羥乙基乙二胺三乙酸銨；甲基甘氨酸二乙酸銨；次氮基三乙酸三銨；過硫酸銨；硫酸銨；碳酸銨；硝酸銨；雙硼酸銨；氨基甲酸銨；氟化銨；六氟矽酸銨；六氟鈦酸銨；偏鎢酸銨；五硼酸銨；四氟硼酸銨；三氟甲磺酸銨；反式-1,2-亞環己基二次氮基四乙酸四甲基銨；乙二胺四乙酸四甲基銨。 The activator may be selected from the following: ammonium methanesulfonate; ammonium dihydrogen phosphate ((NH ₄ )H ₂ PO ₄ ); diammonium hydrogen phosphate (diammonium phosphate, (NH ₄ ) ₂ HPO ₄ ); ammonium phosphate (( NH ₄ ) ₃ PO ₄ ); Triammonium citrate; Ammonium acetate; Ammonium EDTA; Tetraammonium EDTA; Ammonium diethylenetriaminepentaacetate; Ammonium hydroxyethylethylenediaminetriacetate; Ammonium methylglycine diacetate; Triammonium nitrilotriacetate; Ammonium persulfate; Ammonium sulfate; Ammonium carbonate; Ammonium nitrate; Diboronic acid Ammonium; Ammonium carbamate; Ammonium fluoride; Ammonium hexafluorosilicate; Ammonium hexafluorotitanate; Ammonium metatungstate; Ammonium pentaborate; Ammonium tetrafluoroborate; Tetramethylammonium cyclohexylenedinitrotetraacetate; Tetramethylammonium ethylenediaminetetraacetate.

以組成物的總重量計，存在于本發明的組成物中的活化劑的量的範圍可以是從0.01到3 wt%，優選地從0.1到1 wt%。The amount of activator present in the composition of the invention may range from 0.01 to 3 wt%, preferably from 0.1 to 1 wt%, based on the total weight of the composition.

在優選實施例中，以組成物的總重量計，作為活化劑存在於組成物中的反式-1,2-亞環己基二次氮基四乙酸的量的範圍是從0.01到0.5 wt%，優選地從0.05到0.3 wt%，最優選地從0.08到0.2 wt%。例如，以組成物的總重量計，作為活化劑存在於組成物中的反式-1,2-亞環己基二次氮基四乙酸的量是0.3 wt%。In a preferred embodiment, the amount of trans-1,2-cyclohexylidenedinitrotetraacetic acid present in the composition as an activator ranges from 0.01 to 0.5 wt%, based on the total weight of the composition , preferably from 0.05 to 0.3 wt%, most preferably from 0.08 to 0.2 wt%. For example, the amount of trans-1,2-cyclohexylidenenitrilotetraacetic acid present in the composition as an activator is 0.3 wt%, based on the total weight of the composition.

可部分地與水混溶的有機溶劑可用於降低表面張力並增加表面潤濕，而不會出現與典型表面活性劑相關的任何缺點（例如對表面的強物理吸附），並有助於溶解有機聚合物和聚合物殘渣（例如包含-CFx ，-CHx）。特別選擇乙二醇醚作為有機溶劑並且可以選自以下項：丁基乙二醇（BG）、丁基二甘醇（BDG）、丁基三甘醇、正己基二甘醇、正己基乙二醇、2-己氧基-1-乙醇、四氫糠醇、乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、乙二醇二甲醚、乙二醇二***、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丙醚、二乙二醇單異丙醚二乙二醇單丁醚、二乙二醇單異丁醚、二乙二醇單苄醚、二乙二醇二甲醚、二乙二醇二***、三乙二醇單甲醚、三乙二醇二甲醚、聚乙二醇單甲醚、二乙二醇甲***、三乙二醇乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚、丙二醇二甲醚、丙二醇單丁醚、丙二醇、單丙醚、二丙二醇單甲醚、二丙二醇單丙醚、二丙二醇單異丙醚、二亞丙基單丁醚、二丙二醇二異丙醚、三丙二醇單甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇。Partially water-miscible organic solvents can be used to lower surface tension and increase surface wetting without any of the disadvantages associated with typical surfactants (such as strong physical adsorption to the surface) and help dissolve organic Polymers and polymer residues (e.g. containing -CFx, -CHx). Glycol ethers are especially chosen as organic solvents and may be selected from the following: butyl glycol (BG), butyl diglycol (BDG), butyl triethylene glycol, n-hexyl diglycol, n-hexyl Alcohol, 2-hexyloxy-1-ethanol, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol Alcohol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether , Triethylene glycol ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol, monopropyl ether, dipropylene glycol monomethyl ether , dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol diisopropyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-butanol, 2-methoxy 1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane and 2-(2-butoxyethoxy)ethanol.

以組成物的總重量計，存在于本發明的組成物中的乙二醇醚的量的範圍可以是從1到60 wt%，優選地從10到50 wt%。The amount of glycol ether present in the composition of the invention may range from 1 to 60 wt%, preferably from 10 to 50 wt%, based on the total weight of the composition.

在優選實施例中，以組成物的總重量計，作為乙二醇醚存在於組成物中的BDG的量的範圍是從1到60 wt%，優選地從10到55 wt%，最優選地從15到45 wt%。例如，以組成物的總重量計，作為活化劑存在於組成物中的BDG的量是30 wt%。In a preferred embodiment, the amount of BDG present in the composition as a glycol ether ranges from 1 to 60 wt%, preferably from 10 to 55 wt%, based on the total weight of the composition, most preferably From 15 to 45 wt%. For example, the amount of BDG present in the composition as an activator is 30 wt%, based on the total weight of the composition.

任選地，組成物中還使用非質子溶劑以説明溶解組成物中的其它組分並提高有機殘渣從晶片表面的移除效率和溶解度。非質子溶劑（如果存在）可以選自以下項：二甲基亞碸（DMSO）、環丁碸、碳酸亞丙酯、二甲基乙醯胺（DMAc）、N-甲基-2-吡咯烷酮（NMP）、二甲基甲醯胺（DMF）或其混合物。Optionally, an aprotic solvent is also used in the composition to illustrate the dissolution of other components in the composition and to enhance the removal efficiency and solubility of organic residues from the wafer surface. Aprotic solvents, if present, may be selected from the following: dimethylsulfoxide (DMSO), cyclobutene, propylene carbonate, dimethylacetamide (DMAc), N-methyl-2-pyrrolidone ( NMP), dimethylformamide (DMF) or mixtures thereof.

以組成物的總重量計，非質子溶劑（如果存在的話）存在于本發明的組成物中的量可以從1到50 wt%，優選地從5到25 wt%。Aprotic solvents, if present, may be present in the compositions of the invention in amounts from 1 to 50 wt%, preferably from 5 to 25 wt%, based on the total weight of the composition.

在優選實施例中，以組成物的總重量計，作為溶劑存在於組成物中的DMSO的量的範圍是從1到50 wt%，優選地從3到20 wt%，最優選地從5到15 wt%。例如，以組成物的總重量計，作為活化劑存在於組成物中的BDG的量是30 wt%。In a preferred embodiment, the amount of DMSO present in the composition as a solvent ranges from 1 to 50 wt%, preferably from 3 to 20 wt%, most preferably from 5 to 20 wt%, based on the total weight of the composition. 15 wt%. For example, the amount of BDG present in the composition as an activator is 30 wt%, based on the total weight of the composition.

餘下的是水。The rest is water.

在本發明的另一個實施例中，可以將氧化劑加入到包含a）有機胺、b）一種或多種抑制劑、c）一種或多種緩衝劑、d）活化劑、e）一種或多種乙二醇醚、f）任選的非質子溶劑和g）水的組成物中，以形成製劑。氧化劑可以選自過氧化氫（H ₂O ₂）、臭氧水、過硫酸。 In another embodiment of the present invention, an oxidizing agent may be added to a compound containing a) an organic amine, b) one or more inhibitors, c) one or more buffers, d) an activator, e) one or more glycols ether, f) an optional aprotic solvent, and g) water to form a formulation. The oxidizing agent may be selected from hydrogen peroxide (H ₂ O ₂ ), ozone water, persulfuric acid.

氧化劑可以以以下範圍的體積比（包含組分a）到g）的組成物與氧化劑之比）添加：從65：1到1：5（約從0.51到26.2 wt%），優選地從33：1到1：52（約從1到21.3 wt%），最優選地從22：1到1：1（約從1.5到16.2 wt%）。The oxidizing agent may be added in a volume ratio (composition to oxidizing agent ratio comprising components a) to g) of: from 65:1 to 1:5 (approximately from 0.51 to 26.2 wt%), preferably from 33: 1 to 1:52 (approximately from 1 to 21.3 wt%), most preferably from 22:1 to 1:1 (approximately from 1.5 to 16.2 wt%).

在本申請的另一個實施例中，提供了一種試劑盒。所述試劑盒由A）組成物和B）氧化劑構成，所述組成物包含：a）有機胺；b）一種或多種抑制劑；c）一種或多種緩衝劑；d）活化劑；e）一種或多種乙二醇醚；f）任選的非質子溶劑和g）水。In another embodiment of the present application, a kit is provided. The kit is composed of A) a composition and B) an oxidant, and the composition includes: a) an organic amine; b) one or more inhibitors; c) one or more buffers; d) an activator; or multiple glycol ethers; f) an optional aprotic solvent and g) water.

在半導體/IC生產過程中，該試劑盒可用於分別調節Cu/Co/Ru和TiN的蝕刻速率，以及從晶片上移除有機聚合物和殘渣。During semiconductor/IC production, the kit can be used to adjust the etch rate of Cu/Co/Ru and TiN respectively, and to remove organic polymers and residues from wafers.

下面進行的實驗和實例分別用來說明TiN和Cu/Co/Ru的蝕刻和蝕刻速率，並顯示有機聚合物和殘渣的移除。The following experiments and examples were performed to illustrate the etch and etch rates of TiN and Cu/Co/Ru, respectively, and to show the removal of organic polymers and residues.

實驗：experiment:

A.蝕刻速率實驗：A. Etching rate experiment:

步驟1.不帶圖案的晶片（Cu/Co/Ru，TiN，低-k）或圖案化晶片選自商業來源。Step 1. Unpatterned wafers (Cu/Co/Ru, TiN, low-k) or patterned wafers were selected from commercial sources.

步驟2.如圖3所示，將晶片破碎成較小的試樣51。Step 2. Break the wafer into smaller specimens 51 as shown in FIG. 3 .

步驟3.測量適當材料的膜厚度：Step 3. Measure the film thickness of the appropriate material:

1.對於金屬，使用4點探針或X射線螢光（XRF）來測量層厚度；1. For metals, use a 4-point probe or X-ray fluorescence (XRF) to measure layer thickness;

2.對於非金屬，使用橢圓偏光法來測量膜厚度。2. For non-metals, use ellipsometry to measure film thickness.

步驟4.如下所述製備製劑52。Step 4. Formulation 52 was prepared as described below.

步驟5.將製劑52放入熱迴圈罐中以達到穩定的目標溫度；所使用的溫度與常用工業過程中使用的溫度（約40到70℃）相似。使用機械攪拌器攪拌溶液。Step 5. Place the formulation 52 in a thermocycler to achieve a stable target temperature; the temperature used is similar to that used in common industrial processes (approximately 40 to 70°C). The solution was stirred using a mechanical stirrer.

步驟6.試樣被固定在機械保持架。Step 6. The specimen is fixed in the mechanical holder.

步驟7.如圖3所示，將試樣與溶液接觸一段時間（通常10分鐘）。Step 7. As shown in Figure 3, contact the sample with the solution for a period of time (typically 10 minutes).

步驟8.經過一定時間後，溶液與試樣之間的接觸被切斷，試樣用超純水或IPA或水/IPA混合物清理約2到5分鐘。Step 8. After a certain period of time, the contact between the solution and the sample is cut off, and the sample is cleaned with ultrapure water or IPA or a water/IPA mixture for about 2 to 5 minutes.

步驟9.將試樣用 N ₂氣體乾燥並進行檢查以確保表面上沒有水殘留。 Step 9. Dry the specimen with _N2 gas and check to ensure that no water remains on the surface.

步驟10.如步驟3中所述測量殘渣厚度。Step 10. Measure residue thickness as described in Step 3.

步驟11.如下所述計算蝕刻速率。Step 11. Calculate the etch rate as described below.

例如，當反應前的厚度為330埃（A），反應後的厚度為300埃，反應時間為10分鐘時，蝕刻速率計算如下：蝕刻速率=（330-300/10 = 3Å/分鐘 For example, when the thickness before the reaction is 330 Å (A), the thickness after the reaction is 300 Å, and the reaction time is 10 minutes, the etching rate is calculated as follows: Etch Rate = (330-300/10 = 3Å/min

B.圖案化的晶片表面殘渣組成物評估B. Patterned Wafer Surface Residue Composition Evaluation

步驟與A相同，但未執行步驟3、10和11。The steps are the same as A, but steps 3, 10 and 11 are not performed.

實例：Example:

給出以下實例以允許更好地理解本公開。這些實例不應被解釋為在任何方面縮小本公開的範圍。The following examples are given to allow a better understanding of the present disclosure. These examples should not be construed as narrowing the scope of the present disclosure in any way.

除了以包含組分a）到g）的組成物與氧化劑的體積比加入氧化劑之外，本說明書中的所有百分比資料都是以組成物的總重量計的重量百分比。不言而喻，組成物中添加的組分a）到g）的量加起來為100%。All percentage data in this specification are percentages by weight based on the total weight of the composition, except that the oxidizing agent is added in a volume ratio of the composition comprising components a) to g) to the oxidizing agent. It goes without saying that the amounts of components a) to g) added to the composition add up to 100%.

按照下文所概述在上述的步驟之後進行各種實例以說明本公開以及現有技術與本公開之間的比較。Various examples were carried out following the steps described above as outlined below to illustrate the present disclosure and a comparison between the prior art and the present disclosure.

實例1到6Instances 1 to 6

有機胺的作用The role of organic amines

在實例1到6中，乙二胺四乙酸四銨用作活化劑，BDG用作乙二醇醚，DMSO用作非質子溶劑，BTA用作抑制劑，而在實例1-2、3-4和5-6中，咪唑、1-甲基嗎啉-4-氧化物或1,3,5-三(二甲基氨基丙基)-均六氫三嗪分別用作有機胺。餘下的是水。表1 實例1 實例2 咪唑 0.1 0.2 反式-1,2-亞環己基二次氮基四乙酸四銨；(NH4)4-CDTA 0.1 0.1 BDG 35 35 DMSO 10 10 BTA 4 4 組成物：H ₂O ₂體積比 1:1 1:1 Cu E/R (Å/min) 4.2 4.2 Co E/R (Å/min) 1.2 2.1 TiN E/R (Å/min) 165 195 實例3 實例4 4-甲基嗎啉4-氧化物 10 12 乙二胺四乙酸四銨 0.1 0.1 BDG 30 30 DMSO 10 10 BTA 4 4 組成物：H ₂O ₂體積比 1:1 1:1 Cu E/R (Å/min) 4 4.2 Co E/R (Å/min) 0.2 0.2 TiN E/R (Å/min) 168 174 實例5 實例6 1,3,5-三(二甲基氨基丙基)-均六氫三嗪 3 5 乙二胺四乙酸四銨 0.1 0.1 BDG 30 30 DMSO 10 10 BTA 4 4 組成物：H ₂O ₂體積比 1:1 1:1 Cu E/R (Å/min) 4.2 4.2 Co E/R (Å/min) 0.4 0.6 TiN E/R (Å/min) 168 174 In examples 1 to 6, tetraammonium edetate was used as activator, BDG was used as glycol ether, DMSO was used as aprotic solvent, and BTA was used as inhibitor, while in examples 1-2, 3-4 In and 5-6, imidazole, 1-methylmorpholine-4-oxide or 1,3,5-tris(dimethylaminopropyl)-shexahydrotriazine were used as the organic amine, respectively. The rest is water. Table 1 Example 1 Example 2 imidazole 0.1 0.2 trans-1,2-Cyclohexylidenedinitrotetraammonium tetraacetate; (NH4)4-CDTA 0.1 0.1 BDG 35 35 DMSO 10 10 BTA 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 Cu E/R (Å/min) 4.2 4.2 Co E/R (Å/min) 1.2 2.1 TiN E/R (Å/min) 165 195 Example 3 Example 4 4-Methylmorpholine 4-oxide 10 12 Tetraammonium EDTA 0.1 0.1 BDG 30 30 DMSO 10 10 BTA 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 Cu E/R (Å/min) 4 4.2 Co E/R (Å/min) 0.2 0.2 TiN E/R (Å/min) 168 174 Example 5 Example 6 1,3,5-tris(dimethylaminopropyl)-hexahydrotriazine 3 5 Tetraammonium EDTA 0.1 0.1 BDG 30 30 DMSO 10 10 BTA 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 Cu E/R (Å/min) 4.2 4.2 Co E/R (Å/min) 0.4 0.6 TiN E/R (Å/min) 168 174

表1中的結果表明，TiN E/R隨著有機胺的量增加，並且使用合適的有機胺可以獲得最小的Co和Cu E/R（Å/min）。The results in Table 1 show that the TiN E/R increases with the amount of organic amine, and the smallest Co and Cu E/R (Å/min) can be obtained with the appropriate organic amine.

實例7-17Example 7-17

活化劑的作用The role of activators

在實例7-17中，4-甲基嗎啉4-氧化物用作有機胺，BDG用作乙二醇醚，DMSO用作非質子溶劑，BTA用作抑制劑，而在實例7-9、10-11、12-13、14-15和16-17中，分別使用乙二胺四乙酸四銨、反式-1,2-亞環己基二次氮基四乙酸四銨、檸檬酸三銨、乙酸銨或磷酸氫二銨作為活化劑。餘下的是水。表2 實例7 實例8 實例9 4-甲基嗎啉4-氧化物 10 10 10 乙二胺四乙酸四銨 0 0.1 0.3 BDG 30 30 30 DMSO 10 10 10 BTA 4 4 4 組成物：H ₂O ₂體積比 1:1 1:1 1:1 Cu E/R (Å/min) 3.1 4.3 4.5 Co E/R (Å/min) 1.6 2.1 2.4 TiN E/R (Å/min) 100 168 220 實例10 實例11 4-甲基嗎啉4-氧化物 10 10 反式-1,2-亞環己基二次氮基四乙酸四銨 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 組成物：H ₂O ₂體積比 1:1 1:1 Cu E/R (Å/min) 4 4.2 Co E/R (Å/min) 2.1 2.4 TiN E/R (Å/min) 173 232 實例12 實例13 4-甲基嗎啉4-氧化物 10 10 檸檬酸三銨 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 組成物：H ₂O ₂體積比 1:1 1:1 Cu E/R (Å/min) 5.2 5.4 Co E/R (Å/min) 2.5 3.1 TiN E/R (Å/min) 145 157 實例14 實例15 4-甲基嗎啉4-氧化物 10 10 乙酸銨 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 組成物：H ₂O ₂體積比 1:1 1:1 Cu E/R (Å/min) 3.6 3.8 Co E/R (Å/min) 1.9 2.3 TiN E/R (Å/min) 155 192 實例16 實例17 4-甲基嗎啉4-氧化物 10 10 磷酸氫二銨 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 組成物：H ₂O ₂體積比 1:1 1:1 Cu 3.5 4.5 Co 1.8 2.1 TiN 157 201 In example 7-17, 4-methylmorpholine 4-oxide is used as organic amine, BDG is used as glycol ether, DMSO is used as aprotic solvent, and BTA is used as inhibitor, and in example 7-9, In 10-11, 12-13, 14-15 and 16-17, tetraammonium ethylenediamine tetraacetate, trans-1,2-cyclohexylidene dinitrotetraammonium tetraacetate and triammonium citrate were used respectively , ammonium acetate or diammonium hydrogen phosphate as an activator. The rest is water. Table 2 Example 7 Example 8 Example 9 4-Methylmorpholine 4-oxide 10 10 10 Tetraammonium EDTA 0 0.1 0.3 BDG 30 30 30 DMSO 10 10 10 BTA 4 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 1:1 Cu E/R (Å/min) 3.1 4.3 4.5 Co E/R (Å/min) 1.6 2.1 2.4 TiN E/R (Å/min) 100 168 220 Example 10 Example 11 4-Methylmorpholine 4-oxide 10 10 tetraammonium trans-1,2-cyclohexylidenedinitrotetraacetate 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 Cu E/R (Å/min) 4 4.2 Co E/R (Å/min) 2.1 2.4 TiN E/R (Å/min) 173 232 Example 12 Example 13 4-Methylmorpholine 4-oxide 10 10 triammonium citrate 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 Cu E/R (Å/min) 5.2 5.4 Co E/R (Å/min) 2.5 3.1 TiN E/R (Å/min) 145 157 Example 14 Example 15 4-Methylmorpholine 4-oxide 10 10 Ammonium acetate 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 Cu E/R (Å/min) 3.6 3.8 Co E/R (Å/min) 1.9 2.3 TiN E/R (Å/min) 155 192 Example 16 Example 17 4-Methylmorpholine 4-oxide 10 10 Diammonium hydrogen phosphate 0.1 0.3 BDG 30 30 DMSO 10 10 BTA 4 4 Composition: H ₂ O ₂ volume ratio 1:1 1:1 Cu 3.5 4.5 co 1.8 2.1 TiN 157 201

表2中的結果表明，當不使用活化劑時TiN E/R非常低（實例7），並且隨著活化劑量的增加，TiN E/R顯著增加。The results in Table 2 show that the TiN E/R is very low when no activator is used (Example 7), and the TiN E/R increases significantly with increasing activator dose.

實例18-24Examples 18-24

抑制劑的作用The role of inhibitors

在實例18-24中，使用4-甲基嗎啉4-氧化物作為有機胺，使用反式-1,2-亞環己基二次氮基四乙酸四銨作為活化劑，使用BDG作為乙二醇醚，使用DMSO作為非質子性溶劑，而BTA、N,N-雙(2-乙基己基)-4-甲基-1H-苯並***-1-甲胺、N,N-雙(2-乙基己基)-5-甲基-1H-苯並***-1-甲胺、2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇和6-甲基-苯並***中的一個或多個分別用作抑制劑。餘下的是水。表3 實例18 實例19 實例20 實例21 實例22 實例23 實例24 4-甲基嗎啉4-氧化物 10 10 10 10 10 10 10 反式-1,2-亞環己基二次氮基四乙酸四銨 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BDG 30 30 30 30 30 30 30 DMSO 10 10 10 10 10 10 10 BTA 4 1 0 0 1 1 1 N,N-雙(2-乙基己基)-4-甲基-1H-苯並***-1-甲胺 0 0.1 0.1 0.2 0.2 0 0 N,N-雙(2-乙基己基)-5-甲基-1H-苯並***-1-甲胺 0 0 0.2 0.2 0.2 0 0 2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇 0 0 0 0 0 0.2 0.2 6-甲基-苯並*** 0 0 0 0 0.5 0 0.5 組成物：H ₂O ₂體積比 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Cu (Å/min) 4 2 0.8 0.6 0.2 0.2 0.2 Co (Å/min) 2.1 1.2 0.2 0.2 0.2 0.2 0.1 Ru (Å/min) 0 0 0 0 0 0 0 TiN (Å/min) 173 175 168 170 177 181 181 In Examples 18-24, 4-methylmorpholine 4-oxide was used as the organic amine, trans-1,2-cyclohexylidenedinitrotetraammonium tetraacetate was used as the activator, and BDG was used as the Alcohol ethers, using DMSO as an aprotic solvent, while BTA, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine, N,N-bis( 2-Ethylhexyl)-5-methyl-1H-benzotriazole-1-methanamine, 2,2'-[[(5-methyl-1H-benzotriazol-1-yl)methyl One or more of ]imino]bisethanol and 6-methyl-benzotriazole are used as inhibitors, respectively. The rest is water. table 3 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 4-Methylmorpholine 4-oxide 10 10 10 10 10 10 10 tetraammonium trans-1,2-cyclohexylidenedinitrotetraacetate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 BDG 30 30 30 30 30 30 30 DMSO 10 10 10 10 10 10 10 BTA 4 1 0 0 1 1 1 N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methylamine 0 0.1 0.1 0.2 0.2 0 0 N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methylamine 0 0 0.2 0.2 0.2 0 0 2,2'-[[(5-Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol 0 0 0 0 0 0.2 0.2 6-Methyl-benzotriazole 0 0 0 0 0.5 0 0.5 Composition: H ₂ O ₂ volume ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 Cu (Å/min) 4 2 0.8 0.6 0.2 0.2 0.2 Co (Å/min) 2.1 1.2 0.2 0.2 0.2 0.2 0.1 Ru (Å/min) 0 0 0 0 0 0 0 TiN (Å/min) 173 175 168 170 177 181 181

表3中的結果表明，Cu/Co E/R隨著抑制劑組合的不同而顯著降低，同時保持類似的TiN E/R。沒有檢測到Ru E/R。也就是說，如果使用適當的抑制劑組合，則可以在不損害TiN E/R的情況下實現Cu/Co/Ru的保護。The results in Table 3 show that Cu/Co E/R decreases significantly with different inhibitor combinations while maintaining similar TiN E/R. Ru E/R was not detected. That is, the protection of Cu/Co/Ru can be achieved without compromising the TiN E/R if an appropriate combination of inhibitors is used.

實例25-28Examples 25-28

緩衝劑的作用The role of buffer

在實例25-28中，使用4-甲基嗎啉4-氧化物作為有機胺，使用反式-1,2-亞環己基二次氮基四乙酸四銨作為活化劑，使用BDG作為二醇醚，使用DMSO作為非質子性溶劑，使用BTA、2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇和5-甲基-苯並***作為抑制劑，而使用TMAH（四甲基氫氧化銨）、TEAH（四乙基氫氧化銨）、氫氧化銨、二甘醇胺和三甘醇胺中的一種或多種作為緩衝劑。餘下的是水。表4 實例25 實例26 實例27 實例28 4-甲基嗎啉4-氧化物 10 10 10 10 四銨反式-1,2-亞環己基二次氮基四乙酸 0.1 0.1 0.1 0.1 TMAH（四甲基氫氧化銨） 0 0 0 0 TEAH（四乙基氫氧化銨） 0 0 0 0 氫氧化銨 0 0.2 0 0 二甘醇胺 0 0 0.48 0 三甘醇胺 0 0 0 0.42 BDG 30 30 30 30 DMSO 10 10 10 10 BTA 1 1 1 1 2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇 0.2 0.2 0.2 0.2 6-甲基-苯並*** 0.5 0.5 0.5 0.5 組成物：H ₂O ₂體積比 1:1 1:1 1:1 1:1 pH 6.3 7.1 7.1 7.1 Cu (Å/min) 0.2 0.2 1.5 1.2 Co (Å/min) 0.1 0.1 1.8 1.3 Ru (Å/min) 0 0 0 0 TiN (Å/min) 181 246 210 210 In Examples 25-28, 4-methylmorpholine 4-oxide was used as the organic amine, tetraammonium trans-1,2-cyclohexylidenedinitrotetraacetate was used as the activator, and BDG was used as the diol Ether, using DMSO as the aprotic solvent, using BTA, 2,2'-[[(5-methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol and 5-methyl - Benzotriazole as inhibitor, while one or more of TMAH (tetramethylammonium hydroxide), TEAH (tetraethylammonium hydroxide), ammonium hydroxide, diglycolamine and triethyleneglycolamine are used as buffer. The rest is water. Table 4 Example 25 Example 26 Example 27 Example 28 4-Methylmorpholine 4-oxide 10 10 10 10 Tetraammonium trans-1,2-cyclohexylenedinitrotetraacetic acid 0.1 0.1 0.1 0.1 TMAH (tetramethylammonium hydroxide) 0 0 0 0 TEAH (Tetraethylammonium Hydroxide) 0 0 0 0 Ammonium hydroxide 0 0.2 0 0 diglycolamine 0 0 0.48 0 triethylene glycol amine 0 0 0 0.42 BDG 30 30 30 30 DMSO 10 10 10 10 BTA 1 1 1 1 2,2'-[[(5-Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol 0.2 0.2 0.2 0.2 6-Methyl-benzotriazole 0.5 0.5 0.5 0.5 Composition: H ₂ O ₂ volume ratio 1:1 1:1 1:1 1:1 pH 6.3 7.1 7.1 7.1 Cu (Å/min) 0.2 0.2 1.5 1.2 Co (Å/min) 0.1 0.1 1.8 1.3 Ru (Å/min) 0 0 0 0 TiN (Å/min) 181 246 210 210

表4中的結果表明，當不使用緩衝劑時pH顯著下降（實例25），這也導致TiN E/R的下降。此外，如果使用緩衝劑的適當組合，則可以實現Cu/Co/Ru和良好的TiN E/R保護。The results in Table 4 show that the pH drops significantly when no buffer is used (Example 25), which also leads to a drop in TiN E/R. Furthermore, Cu/Co/Ru and good TiN E/R protection can be achieved if an appropriate combination of buffers is used.

實例29-34Examples 29-34

組成物：H ₂O ₂體積比的作用 Composition: Effect of H ₂ O ₂ Volume Ratio

在實例29-34中，使用4-甲基嗎啉4-氧化物作為有機胺，使用反式-1,2-亞環己基二次氮基四乙酸四銨作為活化劑，使用BDG作為乙二醇醚，使用DMSO作為非質子溶劑，BTA用作抑制劑，並且不使用緩衝劑。餘下的是水。表5 實例29 實例30 實例31 實例32 實例33 實例34 4-甲基嗎啉4-氧化物 10 10 10 10 10 10 反式-1,2-亞環己基二次氮基四乙酸四銨 0.2 0.2 0.2 0.2 0.2 0.2 BDG 35 35 35 35 35 35 DMSO 10 10 10 10 10 10 BTA 1.5 1.5 1.5 1.5 1.5 1.5 組成物：H ₂O ₂體積比 22:1 5:1 2:1 1:1 1:2 1:5 pH 7 6.7 6.5 6.3 6.3 6.2 Cu 0.1 0.3 0.8 1.2 2.1 2.3 Co 0.1 0.7 0.9 1.3 1.8 2.5 Ru (Å/min) 0 0 0 0 0 0 TiN 15 61 98 110 108 93 In Examples 29-34, 4-methylmorpholine 4-oxide was used as the organic amine, trans-1,2-cyclohexylidenedinitrotetraammonium tetraacetate was used as the activator, and BDG was used as the Alcohol ethers, using DMSO as the aprotic solvent, BTA as the inhibitor, and no buffer. The rest is water. table 5 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 4-Methylmorpholine 4-oxide 10 10 10 10 10 10 tetraammonium trans-1,2-cyclohexylidenedinitrotetraacetate 0.2 0.2 0.2 0.2 0.2 0.2 BDG 35 35 35 35 35 35 DMSO 10 10 10 10 10 10 BTA 1.5 1.5 1.5 1.5 1.5 1.5 Composition: H ₂ O ₂ volume ratio 22:1 5:1 2:1 1:1 1:2 1:5 pH 7 6.7 6.5 6.3 6.3 6.2 Cu 0.1 0.3 0.8 1.2 2.1 2.3 co 0.1 0.7 0.9 1.3 1.8 2.5 Ru (Å/min) 0 0 0 0 0 0 TiN 15 61 98 110 108 93

表5中的結果表明，TiN E/R隨著體積比中加入的H ₂O ₂量的增加而增加，當組成物/H ₂O ₂比例約為1:1時，可獲得最佳的TiN E/R和Cu/Co/Ru保護。 The results in Table 5 show that TiN E/R _increases with the _amount of _H2O2 added in the volume ratio, and _the best TiN E/R and Cu/Co/Ru protection.

實例35-43Examples 35-43

溶劑的作用The role of solvents

在實例35-43中，使用4-甲基嗎啉4-氧化物作為有機胺，使用反式-1,2-亞環己基二次氮基四乙酸四銨作為活化劑，使用DMSO作為非質子性溶劑，使用BTA、2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇和5-甲基-苯並***作為抑制劑，使用TMAH（四甲基氫氧化銨）、TEAH（四乙基氫氧化銨）和氫氧化銨作為緩衝劑，同時丁基乙二醇、丁基三甘醇、BDG、正己基二甘醇、正己基乙二醇和二丙二醇單甲醚分別用作乙二醇醚。餘下的是水。表6 實例 35 實例 36 實例 37 實例 38 實例 39 實例 40 實例 41 實例 42 實例 43 4-甲基嗎啉4-氧化物 10 10 10 10 10 10 10 10 10 反式-1,2-亞環己基二次氮基四乙酸四銨； 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 TMAH （四甲基氫氧化銨） 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 TEAH（四乙基氫氧化銨） 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 氫氧化銨 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 乙二醇單丁醚 30 0 0 0 0 0 20 0 0 丁基三甘醇 0 30 0 0 0 0 10 0 0 BDG（丁基二甘醇） 0 0 30 0 0 0 10 10 10 正己基二甘醇 0 0 0 20 0 0 0 10 0 正己基乙二醇 0 0 0 0 20 0 0 0 10 二丙二醇單甲醚 0 0 0 0 0 20 0 10 10 DMSO 10 10 10 15 15 15 10 10 10 BTA 1 1 1 1 1 1 1 1 1 2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 6-甲基-苯並*** 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 組成物：H ₂O ₂體積比 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 pH 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 Cu (Å/min) 0.2 0.2 0.2 1.1 1.2 1.2 0.9 0.7 1 Co (Å/min) 0.8 0.6 0.6 0.2 0.7 0.7 1.2 1.2 1.1 Ru (Å/min) 0 0 0 0 0 0 0 0 0 TiN (Å/min) 100 210 192 193 183 178 187 190 211 In Examples 35-43, 4-methylmorpholine 4-oxide was used as the organic amine, tetraammonium trans-1,2-cyclohexylidenedinitrotetraacetate was used as the activator, and DMSO was used as the aprotic solvent, using BTA, 2,2'-[[(5-methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol and 5-methyl-benzotriazole as inhibitors agent, using TMAH (tetramethylammonium hydroxide), TEAH (tetraethylammonium hydroxide) and ammonium hydroxide as buffers, while butyl glycol, butyl triethylene glycol, BDG, n-hexyl diglycol , n-hexyl glycol and dipropylene glycol monomethyl ether were used as glycol ethers, respectively. The rest is water. Table 6 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 4-Methylmorpholine 4-oxide 10 10 10 10 10 10 10 10 10 Trans-1,2-cyclohexylidenedinitrotetraammonium tetraacetate; 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 TMAH (tetramethylammonium hydroxide) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 TEAH (tetraethylammonium hydroxide) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ammonium hydroxide 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Ethylene glycol monobutyl ether 30 0 0 0 0 0 20 0 0 Butyl triethylene glycol 0 30 0 0 0 0 10 0 0 BDG (Butyldiglycol) 0 0 30 0 0 0 10 10 10 n-Hexyl diglycol 0 0 0 20 0 0 0 10 0 n-Hexyl glycol 0 0 0 0 20 0 0 0 10 Dipropylene glycol monomethyl ether 0 0 0 0 0 20 0 10 10 DMSO 10 10 10 15 15 15 10 10 10 BTA 1 1 1 1 1 1 1 1 1 2,2'-[[(5-Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 6-Methyl-benzotriazole 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Composition: H ₂ O ₂ volume ratio 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 1:1 pH 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 6.7 Cu (Å/min) 0.2 0.2 0.2 1.1 1.2 1.2 0.9 0.7 1 Co (Å/min) 0.8 0.6 0.6 0.2 0.7 0.7 1.2 1.2 1.1 Ru (Å/min) 0 0 0 0 0 0 0 0 0 TiN (Å/min) 100 210 192 193 183 178 187 190 211

表6中的結果表明，不同溶劑（特別是乙二醇醚）的組合將導致不同的TiN和Co/Cu E/R。The results in Table 6 show that the combination of different solvents (especially glycol ethers) will lead to different TiN and Co/Cu E/R.

因此，如果使用適當的溶劑組合，可以實現良好的TiN E/R和Cu/Co/Ru的保護。Therefore, good protection of TiN E/R and Cu/Co/Ru can be achieved if an appropriate solvent combination is used.

從上表中的結果可以看出，所使用的組成物允許控制TiN和Co和/或Cu和/或Ru的蝕刻速率比。As can be seen from the results in the table above, the compositions used allow control of the etch rate ratio of TiN and Co and/or Cu and/or Ru.

在本公開中，詞語“一”或“一個”應被理解為包括單數和複數。相反，在適當的情況下，對複數專案的任何提及均應包括單數。In this disclosure, the words "a" or "an" should be understood to include both the singular and the plural. Conversely, any reference to plural items shall include the singular where appropriate.

從以上所述，將會看到，在不脫離本公開的新穎概念的真實精神和範圍的情況下，可以實現許多修改和變化。應該理解的是，對於所示出的具體實施例或實例沒有限制意圖或者應該被推斷為沒有限制。本公開旨在由所附請求項覆蓋落入請求項範圍內的所有這些修改。From the foregoing it will be apparent that many modifications and variations can be made without departing from the true spirit and scope of the novel concepts of the present disclosure. It should be understood that no limitation is intended or should be inferred with respect to the particular embodiment or example shown. This disclosure is intended to cover by the appended claims all such modifications which fall within the scope of the claims.

11:含有C、O、F、Ti和N的殘渣 12:Cu層 13:Co或Ru阻擋層 14:低k材料 15:TiN 51:試樣 52:製劑 11: Residue containing C, O, F, Ti and N 12: Cu layer 13: Co or Ru barrier layer 14: Low-k material 15:TiN 51: Sample 52: preparation

[圖1]示出了第一金屬化層中的晶片上的通用結構，指定了含有C、O、F、Ti和N的殘渣11、Cu層12、Co或Ru阻擋層13、低k材料14和TiN 15。 [圖2]示出了在第一金屬化層中移除含有C、O、F、Ti和N的殘渣11以及部分蝕刻和全部移除TiN 15。 [圖3]示意性地描述了實驗中使用的實驗裝置（厚度測量；蝕刻速率；清潔性能（SEM，TEM，XPS...））。 [Fig. 1] Shows the general structure on a wafer in the first metallization layer, specifying a residue containing C, O, F, Ti, and N 11, a Cu layer 12, a Co or Ru barrier layer 13, a low-k material 14 and TiN 15. [ FIG. 2 ] shows removal of residue 11 containing C, O, F, Ti and N and partial etching and total removal of TiN 15 in the first metallization layer. [Fig. 3] Schematically depicts the experimental setup used in the experiments (thickness measurement; etching rate; cleaning performance (SEM, TEM, XPS...)).

11:含有C、O、F、Ti和N的殘渣 11: Residue containing C, O, F, Ti and N

12:Cu層 12: Cu layer

13:Co或Ru阻擋層 13: Co or Ru barrier layer

14:低k材料 14: Low-k material

15:TiN 15:TiN

Claims

一種組成物，包括： a）有機胺； b）一種或多種抑制劑； c）一種或多種緩衝劑； d）活化劑； e）一種或多種乙二醇醚； f）任選的非質子溶劑；以及 g）水。 A composition comprising: a) Organic amines; b) one or more inhibitors; c) one or more buffers; d) activators; e) one or more glycol ethers; f) an optional aprotic solvent; and g) water.

根據請求項1的組成物，其中所述有機胺能夠選自以下項：1-甲基咪唑；咪唑；吡唑；4-乙醯嗎啉；N-甲醯嗎啉；1,3,5-三(二甲氨基丙基)-均六氫三嗪；4-甲基吡啶N-氧化物；2-甲基吡啶N-氧化物；4-甲氧基吡啶N-氧化物水合物；4-氯吡啶N-氧化物；8-甲基喹啉N-氧化物；1-十二烷胺, N,N-二甲基-N-氧化物；4-甲基嗎啉4-氧化物；1-十四烷胺, N,N-二甲基-N-氧化物；(C10-C16)烷基二甲基氧化胺；(C12-18)烷基二甲基-N-氧化物；吡啶1-氧化物；癸胺, N,N-二甲基-N-氧化物；十六烷胺, N,N-二甲基-N-氧化物，優選地，所述有機胺能夠選自4-甲基嗎啉4-氧化物和1,3,5-三(二甲基氨基丙基)-均六氫三嗪。According to the composition of claim 1, wherein the organic amine can be selected from the following items: 1-methylimidazole; imidazole; pyrazole; 4-acetylmorpholine; N-formylmorpholine; Tris(dimethylaminopropyl)-hexahydrotriazine; 4-picoline N-oxide; 2-picoline N-oxide; 4-methoxypyridine N-oxide hydrate; Chloropyridine N-oxide; 8-methylquinoline N-oxide; 1-dodecylamine, N,N-dimethyl-N-oxide; 4-methylmorpholine 4-oxide; 1 -tetradecylamine, N,N-dimethyl-N-oxide; (C10-C16)alkyldimethylamine oxide; (C12-18)alkyldimethyl-N-oxide; pyridine 1 -oxide; Decylamine, N,N-dimethyl-N-oxide; Hexadecylamine, N,N-dimethyl-N-oxide, preferably, the organic amine can be selected from 4- Methylmorpholine 4-oxide and 1,3,5-tris(dimethylaminopropyl)-shexahydrotriazine.

根據請求項2的組成物，其中以所述組成物的總重量計，所述有機胺能夠存在於所述組成物中的量的範圍是從0.01到25 wt%，優選地從0.1到15 wt%。The composition according to claim 2, wherein the organic amine can be present in the composition in an amount ranging from 0.01 to 25 wt%, preferably from 0.1 to 15 wt%, based on the total weight of the composition %.

根據請求項1的組成物，其中所述抑制劑能夠選自稱為聚乙烯亞胺（A類）、唑類（B類）及其衍生物的化合物類別，其中（A）類聚乙烯亞胺能夠是：BASF Lupasol® FG、G20、G35、G100、PR8515、HF、P、PS、PO100、PN 50、PN 60、SK，且（B）類唑類能夠是：組氨酸，腺苷，腺嘌呤；吡啶；吲唑；2,2'-聯吡啶；4,4'-雙(氯甲基)-2,2'-聯吡啶；1,2,3-***；1,2,4-***；四唑；五唑，1,3,4-噁二唑；噁二唑，1,2,3-噁二唑；1,2,5-噁二唑；1,2,4-噁二唑；噻唑；1,2,3-噻二唑；1,2,4-噻二唑；1,2,5-噻二唑；1,3,4-噻二唑；苯並***（BTA）；5-烷基苯並***（烷基=-C _nH _2n+1，其中n=1-6）；6-烷基苯並***（烷基=-C _nH _2n+1，其中n=1-6）；5-氨基-苯並***；6-氨基-苯並***；1-(甲氧基甲基)-1H-苯並***；1H-苯並***-1-甲醇；1-(氯甲基)-1H-苯並***；5-苯基-苯並***；N,N-雙(2-乙基己基)-4-甲基-1H-苯並***-1-甲胺；N,N-雙(2-乙基己基)-5-甲基-1H-苯並***-1-甲胺；2,2'-[[(5-甲基-1H-苯並***-1-基)甲基]亞氨基]雙乙醇；5-硝基-苯並***；苯並***羧酸；1-氨基-1,2,4-***；羥基苯並***；2-(5-氨基-戊基)-苯並***；1-氨基-1,2,3-***；1-氨基-5-甲基-1,2,3-***；3-氨基-1,2,4-***；5-氨基-1,2,4-***；3-異丙基-1,2,4-***；3,5-二氨基-1,2,4-***；5-苯硫基-苯並***；5-鹵基-苯並***（鹵基= F、Cl、Br或I）；6-鹵基-苯並***（鹵基= F、Cl、Br或I）；萘並***；4-甲基-2-苯基咪唑；5-氨基四唑；戊四唑；5-苯基-1H-四唑；5-苄基-1H-四唑；5-甲基四唑；2-苄基吡啶；2,4-二氨基-6-甲基-1,3,5-三嗪；甲基四唑；咪唑啉酮；1,5-五亞甲基四唑；咪唑啉硫酮；4-氨基-4H-1,2,4-***；苯並噻唑；苯並咪唑。 The composition according to claim 1, wherein said inhibitor can be selected from the class of compounds known as polyethyleneimines (type A), azoles (type B) and their derivatives, wherein (A) type polyethyleneimine can be : BASF Lupasol® FG, G20, G35, G100, PR8515, HF, P, PS, PO100, PN 50, PN 60, SK, and (B) azoles can be: histidine, adenosine, adenine; Pyridine; Indazole; 2,2'-bipyridine;4,4'-bis(chloromethyl)-2,2'-bipyridine;1,2,3-triazole;1,2,4-triazole;Tetrazole; Pentazole, 1,3,4-oxadiazole; Oxadiazole, 1,2,3-oxadiazole; 1,2,5-oxadiazole; 1,2,4-oxadiazole ; Thiazole; 1,2,3-Thiadiazole; 1,2,4-Thiadiazole; 1,2,5-Thiadiazole; 1,3,4-Thiadiazole; Benzotriazole (BTA) ; 5-alkylbenzotriazole (alkyl=-C _n H _2n+1 , where n=1-6); 6-alkylbenzotriazole (alkyl=-C _n H _2n+1 , where n=1-6); 5-amino-benzotriazole; 6-amino-benzotriazole; 1-(methoxymethyl)-1H-benzotriazole; 1H-benzotriazole-1 -methanol; 1-(chloromethyl)-1H-benzotriazole; 5-phenyl-benzotriazole; N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole Triazole-1-methylamine; N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methylamine; 2,2'-[[(5-methyl -1H-Benzotriazol-1-yl)methyl]imino]bisethanol; 5-nitro-benzotriazole; benzotriazole carboxylic acid; 1-amino-1,2,4-triazole ;Hydroxybenzotriazole; 2-(5-amino-pentyl)-benzotriazole; 1-amino-1,2,3-triazole; 1-amino-5-methyl-1,2,3 -triazole; 3-amino-1,2,4-triazole; 5-amino-1,2,4-triazole; 3-isopropyl-1,2,4-triazole; 3,5-di Amino-1,2,4-triazole; 5-phenylthio-benzotriazole; 5-halo-benzotriazole (halo = F, Cl, Br or I); 6-halo-benzene Triazoles (halogen = F, Cl, Br or I); naphthotriazoles; 4-methyl-2-phenylimidazoles; 5-aminotetrazoles; azole; 5-benzyl-1H-tetrazole; 5-methyltetrazole; 2-benzylpyridine; 2,4-diamino-6-methyl-1,3,5-triazine; methyltetrazole ; imidazolinone; 1,5-pentamethylenetetrazole; imidazolinethione; 4-amino-4H-1,2,4-triazole; benzothiazole; benzimidazole.

根據請求項4的組成物，其中以所述組成物的總重量計，所述抑制劑能夠存在於所述組成物中的量的範圍是從0.01到6 wt%，優選地從0.5到2 wt%。The composition according to claim 4, wherein the inhibitor can be present in the composition in an amount ranging from 0.01 to 6 wt%, preferably from 0.5 to 2 wt%, based on the total weight of the composition %.

根據請求項1的組成物，其中所述緩衝劑能夠選自以下項：氫氧化銨；磷酸；四甲基氫氧化銨（TMAH）；四乙基氫氧化銨（TEAH）；四丁基氫氧化銨；甲醇胺（MEA）；乙醇胺（DEA）；三乙醇胺（TEA）；聚乙二醇胺；二甘醇胺；三甘醇胺；1,3,5-三(二甲氨基丙基)-均六氫三嗪。According to the composition of claim 1, wherein the buffering agent can be selected from the following items: ammonium hydroxide; phosphoric acid; tetramethylammonium hydroxide (TMAH); tetraethylammonium hydroxide (TEAH); tetrabutylhydroxide Ammonium; Methanolamine (MEA); Ethanolamine (DEA); Triethanolamine (TEA); Polyethylene glycolamine; Diethylene glycol amine; Triethylene glycol amine; Hexahydrotriazine.

根據請求項6的組成物，其中以所述組成物的總重量計，所述緩衝劑能夠存在于本發明的所述組成物中的量的範圍是從0.01到5 wt%，優選地從0.5到2 wt%。According to the composition of claim 6, wherein based on the total weight of the composition, the buffering agent can be present in the composition of the present invention in an amount ranging from 0.01 to 5 wt%, preferably from 0.5 to 2 wt%.

根據請求項1的組成物，其中所述活化劑能夠選自以下項：甲磺酸銨；磷酸二氫銨（(NH ₄)H ₂PO ₄）；磷酸氫二銨（磷酸二銨，(NH ₄) ₂HPO ₄）；磷酸銨（(NH ₄) ₃PO ₄）；檸檬酸三銨；醋酸銨；乙二胺四乙酸銨；乙二胺四乙酸四銨；反式-1,2-亞環己基二次氮基四乙酸四銨；二亞乙基三胺五乙酸銨；羥乙基乙二胺三乙酸銨；甲基甘氨酸二乙酸銨；次氮基三乙酸三銨；過硫酸銨；硫酸銨；碳酸銨；硝酸銨；雙硼酸銨；氨基甲酸銨；氟化銨；六氟矽酸銨；六氟鈦酸銨；偏鎢酸銨；五硼酸銨；四氟硼酸銨；三氟甲磺酸銨；反式-1,2-亞環己基二次氮基四乙酸四甲基銨；乙二胺四乙酸四甲基銨。 According to the composition of claim 1, wherein the activator can be selected from the following items: ammonium methanesulfonate; ammonium dihydrogen phosphate ((NH ₄ )H ₂ PO ₄ ); diammonium hydrogen phosphate (diammonium phosphate, (NH ₄ ) ₂ HPO ₄ ); Ammonium Phosphate ((NH ₄ ) ₃ PO ₄ ); Triammonium Citrate; Ammonium Acetate; Ammonium EDTA; Tetraammonium cyclohexyldinitrotetraacetate; Ammonium diethylenetriaminepentaacetate; Ammonium hydroxyethylethylenediaminetriacetate; Ammonium methylglycine diacetate; Triammonium nitrilotriacetate; Ammonium persulfate; Ammonium sulfate; Ammonium carbonate; Ammonium nitrate; Ammonium diborate; Ammonium carbamate; Ammonium fluoride; Ammonium hexafluorosilicate; Ammonium hexafluorotitanate; Ammonium metatungstate; Ammonium pentaborate; Ammonium tetrafluoroborate; Trifluoroform Ammonium sulfonate; tetramethylammonium trans-1,2-cyclohexylidenedinitrotetraacetate; tetramethylammonium ethylenediaminetetraacetate.

根據請求項8的組成物，其中以所述組成物的總重量計，所述活化劑能夠存在于本發明的所述組成物中的量的範圍是從0.01到3 wt%，優選地從0.1到1 wt%。According to the composition of claim 8, wherein based on the total weight of the composition, the activator can be present in the composition of the present invention in an amount ranging from 0.01 to 3 wt%, preferably from 0.1 to 1 wt%.

根據請求項1的組成物，其中所述乙二醇醚能夠選自以下項：丁基乙二醇（BG）、丁基二甘醇（BDG）、丁基三甘醇、正己基二甘醇、正己基乙二醇、2-己氧基-1-乙醇、四氫糠醇、乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、乙二醇二甲醚、乙二醇二***、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丙醚、二乙二醇單異丙醚二乙二醇單丁醚、二乙二醇單異丁醚、二乙二醇單苄醚、二乙二醇二甲醚、二乙二醇二***、三乙二醇單甲醚、三乙二醇二甲醚、聚乙二醇單甲醚、二乙二醇甲***、三乙二醇乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚、丙二醇二甲醚、丙二醇單丁醚、丙二醇、單丙醚、二丙二醇單甲醚、二丙二醇單丙醚、二丙二醇單異丙醚、二亞丙基單丁醚、二丙二醇二異丙醚、三丙二醇單甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷和2-(2-丁氧基乙氧基)乙醇。According to the composition of claim 1, wherein the glycol ether can be selected from the following items: butyl glycol (BG), butyl diethylene glycol (BDG), butyl triethylene glycol, n-hexyl diethylene glycol , n-hexyl glycol, 2-hexyloxy-1-ethanol, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol Alcohol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, di Ethylene glycol methyl ethyl ether, triethylene glycol ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol, monopropyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol diisopropyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-butanol , 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane and 2-(2-butoxyethoxy)ethanol.

根據請求項10的組成物，其中以所述組成物的總重量計，所述乙二醇醚能夠存在于本發明的所述組成物中的量的範圍是從1到60 wt%，優選地從10到50 wt%。The composition according to claim 10, wherein the glycol ether can be present in the composition of the present invention in an amount ranging from 1 to 60 wt%, based on the total weight of the composition, preferably From 10 to 50 wt%.

根據請求項1的組成物，其中所述非質子溶劑能夠選自以下項：二甲基亞碸（DMSO）、環丁碸、碳酸亞丙酯、二甲基乙醯胺（DMAc）、N-甲基-2-吡咯烷酮（NMP）、二甲基甲醯胺（DMF）或它們的混合物。According to the composition of claim 1, wherein the aprotic solvent can be selected from the following items: dimethylsulfoxide (DMSO), cyclobutylene, propylene carbonate, dimethylacetamide (DMAc), N- Methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), or mixtures thereof.

根據請求項12的組成物，其中以所述組成物的總重量計，所述非質子溶劑在存在時能夠存在于本發明的所述組成物中的量的範圍是從1到50 wt%，優選地從5到25 wt%。The composition according to claim 12, wherein said aprotic solvent, when present, can be present in said composition of the present invention in an amount ranging from 1 to 50 wt%, based on the total weight of said composition, Preferably from 5 to 25 wt%.

一種根據請求項1到13中任一項的組成物與氧化劑的組合用於調節Cu/Co/Ru和TiN的蝕刻速率和/或移除有機和/或無機殘渣的用途。Use of a composition according to any one of claims 1 to 13 in combination with an oxidizing agent for adjusting the etch rate of Cu/Co/Ru and TiN and/or removing organic and/or inorganic residues.

根據請求項14的用途，其中所述氧化劑能夠選自過氧化氫（H ₂O ₂）、臭氧水、過硫酸，優選地是過氧化氫。 The use according to claim 14, wherein the oxidizing agent can be selected from hydrogen peroxide (H ₂ O ₂ ), ozone water, persulfuric acid, preferably hydrogen peroxide.

根據請求項14的用途，其中所述氧化劑能夠以範圍從65:1到1:5（約0.51到26.2 wt%），優選地從33:1到1:2（大約1到21.3 wt%），最優選地從22:1到1:1（大約從1.5到16.2 wt%）的體積比（所述包含組分a）到g）的組成物與所述氧化劑的體積比）加入。Use according to claim 14, wherein the oxidizing agent can range from 65:1 to 1:5 (about 0.51 to 26.2 wt%), preferably from 33:1 to 1:2 (about 1 to 21.3 wt%), Most preferably it is added in a volume ratio (volume ratio of the composition comprising components a) to g) to the oxidizing agent) of from 22:1 to 1:1 (approximately from 1.5 to 16.2 wt%).

一種試劑盒，包括：根據請求項1到13中任一項的組成物；以及氧化劑。 A test kit comprising: A composition according to any one of claims 1 to 13; and oxidizing agent.

根據請求項17的試劑盒，其中所述氧化劑能夠選自過氧化氫（H ₂O ₂）、臭氧水、過硫酸，優選地是過氧化氫。 The kit according to claim 17, wherein the oxidizing agent can be selected from hydrogen peroxide (H ₂ O ₂ ), ozone water, persulfuric acid, preferably hydrogen peroxide.