TW201934811A - High flatness copper electroplating method and copper electroplating product having immersion in the pretreatment solution performed prior to electroplating so as to enable adsorption of the first leveling agent to obtain the high flatness copper film coating - Google Patents
High flatness copper electroplating method and copper electroplating product having immersion in the pretreatment solution performed prior to electroplating so as to enable adsorption of the first leveling agent to obtain the high flatness copper film coating Download PDFInfo
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
Description
本發明關於一種鍍銅方法及銅電鍍品,更詳細而言,關於一種高平整度銅電鍍方法及銅電鍍品。The present invention relates to a copper plating method and a copper electroplating product, and more specifically, to a high flatness copper plating method and a copper electroplating product.
電鍍是利用從外部供給的電子來電沉積金屬或金屬氧化物的方法。與通常的電化學系統相同地,電鍍系統包括電極、電解質及用於供給電子的電源。為實施銅電鍍,將形成有圖案的基板用作陰極(cathode),將含磷的銅或不溶性物質用作陽極(anode)。電解質基本上包含銅離子,為了降低電解質自身的電阻,而包含硫酸,並且為了改善銅離子和添加劑的吸附性,而包含氯離子等。Electroplating is a method of depositing a metal or a metal oxide using electrons supplied from the outside. Like a common electrochemical system, a plating system includes an electrode, an electrolyte, and a power source for supplying electrons. To perform copper electroplating, a patterned substrate is used as a cathode, and phosphorus-containing copper or an insoluble material is used as an anode. The electrolyte basically contains copper ions. To reduce the resistance of the electrolyte itself, it contains sulfuric acid, and to improve the adsorption of copper ions and additives, it contains chloride ions.
近年來,為了半導體晶片的高性能化及製造費用的節省,對利用面板級封裝(Panel level package;PLP)製程來開發產品的需求增加,從而對實現微間距布線圖案的高平整度鍍膜的技術的要求也增加了。In recent years, in order to improve the performance of semiconductor wafers and save manufacturing costs, the demand for developing products using a panel level package (PLP) process has increased. Technical requirements have also increased.
[先前技術文獻] [專利文獻] 專利文獻1:韓國授權專利第10-1705734號。[Prior Art Document] [Patent Document] Patent Document 1: Korean Granted Patent No. 10-1705734.
[發明所欲解決之課題][Problems to be Solved by the Invention]
本發明所要解決的技術課題在於提供一種高平整度鍍銅方法及銅電鍍品。The technical problem to be solved by the present invention is to provide a high flatness copper plating method and a copper electroplated product.
本發明所要解決的技術課題不限於如上所提及的技術課題,本案所屬技術領域中具有通常知識者可藉由以下的記載明確地理解未提及的其他技術課題。The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and those with ordinary knowledge in the technical field to which this case belongs can clearly understand other technical problems not mentioned by the following description.
[用以解決課題之手段][Means to solve the problem]
為了實現所述技術課題,本發明一實施例提供一種高平整度銅電鍍方法。In order to achieve the technical problem, an embodiment of the present invention provides a high-flatness copper electroplating method.
所述銅電鍍方法可包括:前處理步驟,將基板浸漬於前處理溶液中,所述前處理溶液含第一整平劑(leveling agent)但不含銅前驅體;浸漬步驟,將前處理後的所述基板浸漬於鍍液中,所述鍍液包含所述第一整平劑、第二整平劑、抑制劑、加速劑及銅前驅體;以及電沉積步驟,對浸漬於所述鍍液的基板施加電流,來電沉積銅膜。The copper electroplating method may include a pretreatment step of immersing the substrate in a pretreatment solution, the pretreatment solution contains a first leveling agent but does not contain a copper precursor; the immersion step, after the pretreatment, The substrate is immersed in a plating solution, the plating solution includes the first leveling agent, the second leveling agent, an inhibitor, an accelerator, and a copper precursor; and an electrodeposition step, wherein the substrate is immersed in the plating solution. A current is applied to the liquid substrate to deposit a copper film.
此時,特徵在於,所述基板具有20μm以下的布線間距。In this case, the substrate has a wiring pitch of 20 μm or less.
此時,特徵在於,在所述前處理步驟中,所述第一整平劑以100mg/l至5000mg/l的濃度添加在所述前處理溶液中。At this time, it is characterized in that, in the pretreatment step, the first leveling agent is added to the pretreatment solution at a concentration of 100 mg / l to 5000 mg / l.
此時,特徵在於,所述第一整平劑用於製造凸出的所述銅膜。At this time, it is characterized in that the first leveling agent is used for manufacturing the protruding copper film.
此時,特徵在於,所述第二整平劑用於製造凹陷的所述銅膜。At this time, it is characterized in that the second leveling agent is used for manufacturing the recessed copper film.
此時,特徵在於,在將前處理後的所述基板浸漬於所述鍍液的步驟中,所述第一整平劑以0.1mg/l至1000mg/l的濃度添加在所述鍍液中。At this time, it is characterized in that, in the step of immersing the substrate after the pretreatment in the plating solution, the first leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. .
此時,特徵在於,在將前處理後的所述基板浸漬於所述鍍液的步驟中,所述第二整平劑以0.1mg/l至1000mg/l的濃度添加在所述鍍液中。At this time, it is characterized in that in the step of immersing the substrate after the pretreatment in the plating solution, the second leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. .
此時,所述抑制劑包含聚亞氧烷基二醇、羧甲基纖維素、N-壬基酚聚乙二醇醚、辛二醇二乙二醇醚、油酸聚乙二醇酯、聚乙二醇、聚乙二醇二甲醚、聚乙二醇-嵌段-聚丙二醇-嵌段-聚乙二醇、聚丙二醇、聚乙烯醇、硬脂醇聚乙二醇醚、硬脂酸聚乙二醇酯、3-甲基-1-丁炔-3-醇、3-甲基-戊烯-3-醇、L-乙炔基環己醇、苯丙炔醇、3-苯基-1-丁炔-3-醇、炔丙醇、甲基丁醇-環氧乙烷、2-甲基-4-氯-3-丁炔-2-醇、二甲基己二醇、二甲基己二醇-環氧乙烷、二甲基辛二醇、苯基丁炔醇或1,4-丁二醇二縮水甘油醚。At this time, the inhibitor includes polyoxyalkylene glycol, carboxymethyl cellulose, N-nonylphenol polyethylene glycol ether, octanediol diethylene glycol ether, oleic acid polyethylene glycol ester, Polyethylene glycol, polyethylene glycol dimethyl ether, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol, polypropylene glycol, polyvinyl alcohol, stearyl alcohol polyethylene glycol ether, stearin Acid polyethylene glycol ester, 3-methyl-1-butyn-3-ol, 3-methyl-penten-3-ol, L-ethynylcyclohexanol, phenylpropynol, 3-phenyl 1-butyn-3-ol, propargyl alcohol, methylbutanol-ethylene oxide, 2-methyl-4-chloro-3-butyn-2-ol, dimethylhexanediol, Methylhexylene glycol-ethylene oxide, dimethyl octanediol, phenylbutynol or 1,4-butanediol diglycidyl ether.
此時,所述加速劑包含(O-(二硫代碳酸乙酯)-S-(3-磺丙基)-酯、3-[(氨基-亞氨基甲基)-硫醇]-1-丙磺酸、3-(苯并噻唑-2-巰基)-丙基磺酸、雙-(磺丙基)-二硫化鈉、N,N-二甲基二硫代氨基甲醯基丙磺酸、3,3-硫代雙(1-丙烷磺酸)、2-羥基-3-[三(羥甲基)甲氨基]-1-丙磺酸、2,3-二巰基丙烷丙磺酸鈉、3-巰基-1-丙磺酸、N,N-雙(4-磺丁基)-3,5-二甲基苯胺、2-巰基-5-苯并咪唑磺酸鈉、5,5'-二硫代雙(2-硝基苯甲酸)、DL-半胱氨酸、4-巰基-苯磺酸或5-巰基-1H-四唑-1-甲磺酸。At this time, the accelerator contains (O- (dithiocarbonate) -S- (3-sulfopropyl) -ester, 3-[(amino-iminomethyl) -thiol] -1- Propanesulfonic acid, 3- (benzothiazole-2-mercapto) -propylsulfonic acid, bis- (sulfopropyl) -sodium disulfide, N, N-dimethyldithiocarbamoylpropanesulfonic acid , 3,3-thiobis (1-propanesulfonic acid), 2-hydroxy-3- [tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, sodium 2,3-dimercaptopropanepropanesulfonic acid , 3-mercapto-1-propanesulfonic acid, N, N-bis (4-sulfobutyl) -3,5-dimethylaniline, 2-mercapto-5-benzimidazole sulfonate, 5,5 ' -Dithiobis (2-nitrobenzoic acid), DL-cysteine, 4-mercapto-benzenesulfonic acid or 5-mercapto-1H-tetrazole-1-methanesulfonic acid.
此時,所述加速劑及所述抑制劑分別獨立地具有100g/mol至100,000g/mol範圍的分子量。At this time, the accelerator and the inhibitor each independently have a molecular weight in a range of 100 g / mol to 100,000 g / mol.
此時,其特徵在於,所述加速劑及所述抑制劑分別獨立地以0.1mg/l至1,000mg/l範圍的濃度添加在所述鍍液中。At this time, it is characterized in that the accelerator and the inhibitor are independently added to the plating solution at a concentration ranging from 0.1 mg / l to 1,000 mg / l.
此時,特徵在於,在所述電沉積銅膜的步驟中,以1ASD至15ASD(Ampere per square Decimeter)的電流密度範圍施加電流。At this time, it is characterized in that in the step of electrodepositing the copper film, a current is applied in a current density range of 1 ASD to 15 ASD (Ampere per square Decimeter).
為了實現所述技術課題,本發明一實施例提供一種銅電鍍品,特徵在於,該銅電鍍品藉由所述銅電鍍方法來製造。In order to achieve the technical problem, an embodiment of the present invention provides a copper electroplated product, which is characterized in that the copper electroplated product is manufactured by the copper electroplating method.
[發明功效][Inventive effect]
根據本發明的實施例,將基板浸漬於含第一整平劑但不含銅前驅體的前處理溶液中,使所述第一整平劑吸附在基板上,從而能夠形成高平整度銅鍍膜。According to an embodiment of the present invention, a substrate is immersed in a pre-treatment solution containing a first leveling agent but not containing a copper precursor, and the first leveling agent is adsorbed on the substrate, so that a high-flatness copper plating film can be formed. .
應理解為本發明的效果不限於所述的效果,而是包括可藉由本發明的詳細說明或申請專利範圍中記載的本發明的構成推論出的所有的效果。It should be understood that the effects of the present invention are not limited to the effects described, but include all the effects that can be deduced from the detailed description of the present invention or the constitution of the present invention described in the scope of the patent application.
以下,參照圖式對本發明進行說明。但是,本發明可藉由多種不同的方式實現,因此並不限定於在此說明的實施例。並且,為了明確地說明本發明,省略與說明無關的部分,在整個說明書中對類似的部分標注類似的元件符號。Hereinafter, the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different ways, so it is not limited to the embodiments described here. In addition, in order to clearly explain the present invention, parts irrelevant to the description are omitted, and similar elements are marked with similar elements throughout the specification.
在整個說明書中,記載有某一部分與另一部分“連接(相連、接觸或結合)”時,這不僅包括“直接連接”的情況,還包括中間隔著其他構件“間接連接”的情況。另外,記載有某一部分“包括”某一構件時,除非特別矛盾的記載,則表示還可包括另一構件也就是不排除具有另一構件。Throughout the description, when a part is "connected (connected, contacted, or combined)" with another part, this includes not only the case of "directly connected" but also the case of "indirect connection" with other components in between. In addition, when a certain part “includes” a certain component, unless there is a particularly contradictory record, it means that another component can also be included, that is, it does not exclude having another component.
本說明書中所使用的術語只是為說明特定的實施例而使用,並非限定本發明。關於單數的表述,除在上下文中明確表示不同含義,則均包括複數的表述。應理解的是,本說明書中“包括”或“具有”等術語用於指定說明書中記載的特徵、數位、步驟、動作、構件、配件或它們的組合的存在,而非提前排除一個或以上的其他特徵或數位、步驟、動作、構件、部件或它們的組合的存在或其他可能性。The terms used in the present specification are used to describe specific embodiments, and do not limit the present invention. Regarding the expression of the singular, unless the context clearly indicates different meanings, it includes the expression of the plural. It should be understood that terms such as "including" or "having" in this specification are used to specify the existence of features, digits, steps, actions, components, accessories or combinations thereof described in the specification, rather than excluding one or more of them in advance. Presence or other possibility of other features or digits, steps, actions, components, parts or combinations thereof.
以下,參照圖式,對本發明的實施例進行詳細說明。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
本發明一實施例對高平整度銅電鍍方法進行說明。An embodiment of the present invention describes a high-flatness copper plating method.
圖1是表示本發明一實施例的銅電鍍方法的流程圖。FIG. 1 is a flowchart showing a copper plating method according to an embodiment of the present invention.
參照圖1,所述銅電鍍方法可包括:前處理步驟S100,將基板浸漬於前處理溶液中進行前處理,所述前處理溶液含第一整平劑但不含銅前驅體;浸漬步驟S200,將前處理後的所述基板浸漬於鍍液中,所述鍍液包含所述第一整平劑、第二整平劑、抑制劑、加速劑及銅前驅體;以及電沉積步驟S300,對浸漬於所述鍍液的基板施加電流,來電沉積銅膜。Referring to FIG. 1, the copper electroplating method may include a pre-processing step S100, in which a substrate is immersed in a pre-processing solution, the pre-processing solution contains a first leveling agent but does not contain a copper precursor; the dipping step S200 Immersing the substrate after the pretreatment in a plating solution, the plating solution including the first leveling agent, the second leveling agent, an inhibitor, an accelerator, and a copper precursor; and an electrodeposition step S300, A current is applied to a substrate immersed in the plating solution to deposit a copper film by electric current.
此時,特徵在於,所述基板具有20μm以下的布線間距,以實現移動半導體晶片的高性能化及製造費用的節省。At this time, the substrate is characterized in that the substrate has a wiring pitch of 20 μm or less in order to realize high performance of mobile semiconductor wafers and save manufacturing costs.
此時,在所述前處理步驟S100中,所述第一整平劑發揮介面活性化及引導鍍液浸透至布線內的作用,將鍍液中的電解質均勻供給至基板的表面,從而能夠得到高平整度效果。At this time, in the pre-processing step S100, the first leveling agent functions to activate the interface and guide the plating solution to penetrate into the wiring, and uniformly supplies the electrolyte in the plating solution to the surface of the substrate, thereby enabling Get high flatness effect.
此時,在所述前處理步驟S100中,藉由將基板浸漬於含第一整平劑但不含銅前驅體的前處理溶液中,使所述第一整平劑吸附在基板上,從而能夠形成高平整度銅鍍膜。At this time, in the pre-processing step S100, by immersing the substrate in a pre-treatment solution containing a first leveling agent but not containing a copper precursor, the first leveling agent is adsorbed on the substrate, thereby Able to form high flatness copper plating film.
此時,特徵在於,在所述前處理步驟S100中,所述第一整平劑以100mg/l至5000mg/l的濃度添加在所述前處理溶液中。At this time, it is characterized in that, in the pre-processing step S100, the first leveling agent is added to the pre-processing solution at a concentration of 100 mg / l to 5000 mg / l.
此時,在所述第一整平劑的濃度小於100mg/l的情況下,第一整平劑不能充分滲透至布線內部,因此無法期待第一整平劑對電鍍結果產生影響。At this time, when the concentration of the first leveling agent is less than 100 mg / l, the first leveling agent cannot sufficiently penetrate into the wiring, so it cannot be expected that the first leveling agent will affect the plating result.
此時,在所述第一整平劑的濃度超過5000mg/l的情況下,因吸附第一整平劑過度,可能導致鍍膜不均勻。At this time, when the concentration of the first leveling agent exceeds 5000 mg / l, the first leveling agent is adsorbed excessively, which may cause uneven coating.
此時,特徵在於,在將前處理後的所述基板浸漬於所述鍍液的步驟S200中,所述第一整平劑以0.1mg/l至1000mg/l的濃度添加在所述鍍液中。At this time, it is characterized in that, in step S200 of immersing the substrate after the pretreatment in the plating solution, the first leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. in.
此時,特徵在於,所述第一整平劑用於製造凸出的所述銅膜。At this time, it is characterized in that the first leveling agent is used for manufacturing the protruding copper film.
此時,在基板上形成銅膜的銅電鍍製程中,所述第一整平劑吸附於形成高電流密度的鍍膜的部位,來抑制銅離子的還原,從而改善銅鍍膜的均勻度及平整度,其結果,電鍍後能夠改善圖案的均勻度及平整度。At this time, in the copper electroplating process of forming a copper film on the substrate, the first leveling agent is adsorbed on a portion where a high current density plating film is formed to suppress reduction of copper ions, thereby improving the uniformity and flatness of the copper plating film. As a result, the uniformity and flatness of the pattern can be improved after plating.
此時,特徵在於,在將前處理後的所述基板浸漬於所述鍍液的步驟S200中,所述第二整平劑以0.1mg/l至1000mg/l的濃度添加至所述鍍液中。At this time, it is characterized in that in step S200 of immersing the substrate after the pretreatment in the plating solution, the second leveling agent is added to the plating solution at a concentration of 0.1 mg / l to 1000 mg / l. in.
此時,特徵在於,所述第二整平劑用於製造凹陷的所述銅膜。At this time, it is characterized in that the second leveling agent is used for manufacturing the recessed copper film.
此時,在基板上形成銅膜的銅電鍍製程中,所述第二整平劑吸附於形成高電流密度的鍍膜的部位,來抑制銅離子的還原,從而改善銅鍍膜的均勻度及平整度,其結果,電鍍後能夠改善圖案的均勻度及平整度。At this time, in the copper electroplating process of forming a copper film on the substrate, the second leveling agent is adsorbed on a portion where a high current density plating film is formed to suppress reduction of copper ions, thereby improving the uniformity and flatness of the copper plating film As a result, the uniformity and flatness of the pattern can be improved after plating.
例如,所述第一整平劑可具有以下化學式1的結構。For example, the first leveling agent may have a structure of the following Chemical Formula 1.
[化學式1] [Chemical Formula 1]
此時,R1 作為包含氮、氧、硫、磷中一個或兩個原子的飽和雜環化合物,可包含氮丙啶、環氧乙烷、環硫乙烷、二氮雜環丙烷(diaziridine)、氧雜吖丙啶、雙環氧乙烷、氮雜環丁烷、氧雜環丁烷、硫化環丙烷、二氮雜環丁烷、二氧環丁烷(dioxetane)、二硫雜環丁烷、吡咯烷、硫雜環戊烷、磷醯胺、咪唑烷、吡唑烷、噁唑烷、異噁唑烷、噻唑烷、異噻唑烷、二氧戊環、二硫戊環、呱啶、環氧乙烷、硫代環己烷、磷醯環己烷、呱嗪、嗎啉、硫代嗎啉、二噁烷、二噻烷、氮雜環庚烷、氧雜環庚烷、硫雜環庚烷、高呱嗪、氮雜環辛烷、氧雜環辛烷、硫雜環辛烷、氮雜環壬烷、氧雜環壬烷或硫雜環壬烷。At this time, as a saturated heterocyclic compound containing one or two atoms of nitrogen, oxygen, sulfur, and phosphorus, R 1 may include aziridine, ethylene oxide, episulfide, and diaziridine. , Oxaziridine, dioxirane, azetidine, oxetane, cyclopropane sulfide, diazetidine, dioxetane, dithiatidine Alkane, pyrrolidine, thiacyclopentane, phosphatidamine, imidazolidine, pyrazolidine, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, dioxolane, dithiopentane, pyridine , Ethylene oxide, thiocyclohexane, phosphinocyclohexane, verazine, morpholine, thiomorpholine, dioxane, dithiane, azacycloheptane, oxepane, sulfur Heterane heptane, homopyrazine, azaoctane, oxane, thiaoctane, azetane, oxonane or thianonane.
此時,特徵在於,所述R2 及所述R3 分別為單獨包含氫、醚官能團的碳數1至10個的線型烷基,或者為包含醚官能團的碳數5至20個的分支型烷基。At this time, it is characterized in that the R 2 and the R 3 are each a linear alkyl group having 1 to 10 carbon atoms containing hydrogen and ether functional groups, or a branched type having 5 to 20 carbon atoms including ether functional groups, respectively. alkyl.
此時,特徵在於,所述m為300至4500的整數。At this time, it is characterized in that the m is an integer of 300 to 4500.
此時,所述X可包含氯(Cl)、溴(Br)、碘(I)、硝酸根(NO3 )、硫酸根(SO4 )、碳酸根(CO3 )或羥基(OH)。At this time, the X may include chlorine (Cl), bromine (Br), iodine (I), nitrate (NO 3 ), sulfate (SO 4 ), carbonate (CO 3 ), or hydroxyl (OH).
例如,所述第二整平劑可具有以下化學式2的結構。For example, the second leveling agent may have a structure of the following Chemical Formula 2.
化學式2 Chemical formula 2
此時,特徵在於,所述R4 為包含氫、醚官能團的碳數1至10個的線型烷基,或者為包含醚官能團的碳數5至20個的分支型烷基。At this time, it is characterized in that R 4 is a linear alkyl group containing 1 to 10 carbon atoms containing hydrogen and ether functional groups, or a branched alkyl group containing 5 to 20 carbon atoms containing ether functional groups.
此時,特徵在於,所述R5 包含芳香族烴。In this case, it is characterized in that R 5 contains an aromatic hydrocarbon.
此時,所述R6 為包含氫、碳數1至5個的線型烷基,或者為碳數1至2個的含氮的官能團如腈、亞胺、脲、異氰酸酯、醯胺、胺或肼。At this time, R 6 is a hydrogen-containing linear alkyl group having 1 to 5 carbon atoms, or a nitrogen-containing functional group having 1 to 2 carbon atoms such as nitrile, imine, urea, isocyanate, ammonium, amine, or Hydrazine.
此時,特徵在於,所述R7 為包含氫、醚官能團的碳數1至10個的線型烷基,或者為包含醚官能團的碳數5至20個的分支型烷基。At this time, it is characterized in that R 7 is a linear alkyl group containing 1 to 10 carbon atoms containing hydrogen and ether functional groups, or a branched alkyl group containing 5 to 20 carbon atoms containing ether functional groups.
此時,特徵在於,所述n為50至300的整數。At this time, it is characterized in that the n is an integer of 50 to 300.
此時,所述抑制劑可包含聚亞氧烷基二醇、羧甲基纖維素、N-壬基酚聚乙二醇醚、辛二醇二乙二醇醚、油酸聚乙二醇酯、聚乙二醇、聚乙二醇二甲醚、聚乙二醇-嵌段-聚丙二醇-嵌段-聚乙二醇、聚丙二醇、聚乙烯醇、硬脂醇聚乙二醇醚、硬脂酸聚乙二醇酯、3-甲基-1-丁炔-3-醇、3-甲基-戊烯-3-醇、L-乙炔基環己醇、苯丙炔醇、3-苯基-1-丁炔-3-醇、炔丙醇、甲基丁醇-環氧乙烷、2-甲基-4-氯-3-丁炔-2-醇、二甲基己二醇、二甲基己二醇-環氧乙烷、二甲基辛二醇、苯基丁炔醇或1,4-丁二醇二縮水甘油醚。At this time, the inhibitor may include polyoxyalkylene glycol, carboxymethyl cellulose, N-nonylphenol polyethylene glycol ether, octanediol diethylene glycol ether, and oleic acid polyethylene glycol ester. , Polyethylene glycol, polyethylene glycol dimethyl ether, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol, polypropylene glycol, polyvinyl alcohol, stearyl alcohol polyethylene glycol ether, hard Polyethylene glycol fatty acid, 3-methyl-1-butyn-3-ol, 3-methyl-penten-3-ol, L-ethynylcyclohexanol, phenylpropynol, 3-benzene Methyl-1-butyn-3-ol, propargyl alcohol, methylbutanol-ethylene oxide, 2-methyl-4-chloro-3-butyn-2-ol, dimethylhexanediol, Dimethyl hexanediol-ethylene oxide, dimethyl octanediol, phenylbutynol or 1,4-butanediol diglycidyl ether.
此時,特徵在於,所述抑制劑在銅電鍍製程中抑制銅的還原,且提高鍍液的潤濕性,從而在具有圖案的基板上容易形成銅膜。At this time, the inhibitor is characterized in that the reduction of copper is suppressed in the copper plating process, and the wettability of the plating solution is improved, so that a copper film is easily formed on a substrate having a pattern.
此時,所述加速劑可包含(O-(二硫代碳酸乙酯)-S-(3-磺丙基)-酯、3-[(氨基-亞氨基甲基)-硫醇]-1-丙磺酸、3-(苯并噻唑-2-巰基)-丙基磺酸、雙-(磺丙基)-二硫化鈉、N,N-二甲基二硫代氨基甲醯基丙磺酸、3,3-硫代雙(1-丙烷磺酸)、2-羥基-3-[三(羥甲基)甲氨基]-1-丙磺酸、2,3-二巰基丙烷丙磺酸鈉、3-巰基-1-丙磺酸、N,N-雙(4-磺丁基)-3,5-二甲基苯胺、2-巰基-5-苯并咪唑磺酸鈉、5,5'-二硫代雙(2-硝基苯甲酸)、DL-半胱氨酸、4-巰基-苯磺酸或5-巰基-1H-四唑-1-甲磺酸。At this time, the accelerator may include (O- (dithioethyl carbonate) -S- (3-sulfopropyl) -ester, 3-[(amino-iminomethyl) -thiol] -1 -Propanesulfonic acid, 3- (benzothiazole-2-mercapto) -propylsulfonic acid, bis- (sulfopropyl) -sodium disulfide, N, N-dimethyldithiocarbamoylpropanesulfonic acid Acid, 3,3-thiobis (1-propanesulfonic acid), 2-hydroxy-3- [tris (hydroxymethyl) methylamino] -1-propanesulfonic acid, 2,3-dimercaptopropanepropanesulfonic acid Sodium, 3-mercapto-1-propanesulfonic acid, N, N-bis (4-sulfobutyl) -3,5-dimethylaniline, 2-mercapto-5-benzimidazole sulfonate, 5,5 '-Dithiobis (2-nitrobenzoic acid), DL-cysteine, 4-mercapto-benzenesulfonic acid or 5-mercapto-1H-tetrazole-1-methanesulfonic acid.
此時,特徵在於,所述加速劑作為在銅電鍍製程中降低鍍液的過電壓來生成高密度的核的物質,加速銅還原反應速度,來促進核的生成和成長。At this time, it is characterized in that the accelerator is a substance that reduces the overvoltage of the plating solution to generate high-density nuclei during the copper plating process, accelerates the copper reduction reaction speed, and promotes the generation and growth of nuclei.
此時,在將前處理後的所述基板浸漬於所述鍍液中的步驟S200的鍍液中,所述抑制劑及所述加速劑分別具有100g/mol至100,000g/mol範圍的分子量,可以分別以每升所述鍍液中含0.1mg至1000mg的範圍的濃度來添加。At this time, in the plating solution of step S200 in which the substrate after the pretreatment is immersed in the plating solution, the inhibitor and the accelerator each have a molecular weight in a range of 100 g / mol to 100,000 g / mol, It may be added at a concentration ranging from 0.1 mg to 1000 mg per liter of the plating solution.
此時,特徵在於,在電沉積所述銅膜的步驟S300中,以1ASD至15ASD(Ampere per square Decimeter,安培每平方分米)的電流密度範圍來施加電流。At this time, it is characterized in that, in step S300 of electrodepositing the copper film, a current is applied in a current density range of 1 ASD to 15 ASD (Ampere per square Decimeter, Ampere per square decimeter).
[實施例][Example]
根據本發明的一實施例進行銅電鍍。Copper plating is performed according to an embodiment of the present invention.
首先,準備基板。First, prepare a substrate.
接著,將準備好的基板浸漬於前處理溶液中。Next, the prepared substrate is immersed in a pretreatment solution.
接著,將浸漬於前處理溶液中的基板,浸漬於銅鍍液來進行電鍍。Next, the substrate immersed in the pretreatment solution is immersed in a copper plating solution to perform electroplating.
根據所述一實施例,藉由第一階段至第四階段的多階段的電流施加來實施銅電鍍,以1ASD至15ASD的電流密度範圍來施加電流。According to one embodiment, the copper plating is performed by multi-stage current application from the first stage to the fourth stage, and the current is applied in a current density range of 1 ASD to 15 ASD.
根據所述一實施例,在銅鍍液中,作為抑制劑添加了包含芳香族烴的聚環氧乙烷(poly ethylene oxide)衍生物,作為加速劑添加了包含巰基組的有機化合物。According to the above embodiment, a polyethylene oxide derivative containing an aromatic hydrocarbon is added as an inhibitor to the copper plating solution, and an organic compound containing a mercapto group is added as an accelerator.
根據所述一實施例,在銅鍍液中,第一整平劑的R1 作為包含氮的飽和雜環化合物,是吡咯烷、吡唑烷、噁唑烷、噻唑烷中的一種。第一整平劑的R2 和R3 單獨包含氫。第一整平劑的m為500至1000的整數,第一整平劑的X是鹵族元素中的一種。According to one embodiment, in the copper plating solution, as a saturated heterocyclic compound containing nitrogen, R 1 of the first leveler is one of pyrrolidine, pyrazolidine, oxazolidine, and thiazolidine. R 2 and R 3 of the first leveling agent contain hydrogen alone. The m of the first leveling agent is an integer of 500 to 1000, and X of the first leveling agent is one of halogen elements.
根據所述一實施例,銅鍍液中的第二整平劑的R4 和R6 單獨包含氫。第二整平劑的R5 是苯基或苯甲基中的一種。R7 包含含一個氮的氨基。整平劑的n為80至180的整數。According to one embodiment, R 4 and R 6 of the second leveler in the copper plating solution contain hydrogen alone. R 5 of the second leveler is one of phenyl or benzyl. R 7 contains an amino group containing one nitrogen. The n of the leveling agent is an integer of 80 to 180.
使用光學顯微鏡及雷射掃描共聚焦顯微鏡,對所述一實施例製造的鍍品進行分析。An optical microscope and a laser scanning confocal microscope were used to analyze the plated product manufactured in the first embodiment.
圖2是本發明一實施例的銅電鍍之後使用光學顯微鏡觀測到的圖。FIG. 2 is a diagram observed with an optical microscope after copper plating according to an embodiment of the present invention.
圖3是本發明一實施例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的三維掃描圖。FIG. 3 is a three-dimensional scanning image measured by a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.
圖4是本發明一實施例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的輪廓結果。FIG. 4 is a profile result measured using a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.
參照圖2至圖4,根據本發明一實施例先浸漬於前處理溶液後再進行電鍍時,測得布線內厚度的不均勻度為2.5%。Referring to FIG. 2 to FIG. 4, according to an embodiment of the present invention, when the substrate is immersed in the pretreatment solution and then electroplated, the unevenness of the thickness in the wiring is measured to be 2.5%.
比較例Comparative example
為了與本發明一實施例進行比較,不浸漬於含第一整平劑的前處理溶液而直接進行電鍍。For comparison with an embodiment of the present invention, plating is performed directly without being immersed in a pre-treatment solution containing a first leveling agent.
首先,準備基板。First, prepare a substrate.
接著,將酸洗後的基板浸漬於銅鍍液中來進行電鍍。Next, the pickled substrate is immersed in a copper plating solution to perform electroplating.
根據所述一實施例,藉由第一階段至第四階段的多階段的電流施加來實施銅電鍍,以1ASD至15ASD的電流密度範圍施加電流。According to the embodiment, the copper plating is performed by multi-stage current application from the first stage to the fourth stage, and the current is applied in a current density range of 1 ASD to 15 ASD.
根據所述一實施例,在銅鍍液中,作為抑制劑添加了包含芳香族烴的聚環氧乙烷(poly ethylene oxide)衍生物,作為加速劑添加了包含巰基組的有機化合物。According to the above embodiment, a polyethylene oxide derivative containing an aromatic hydrocarbon is added as an inhibitor to the copper plating solution, and an organic compound containing a mercapto group is added as an accelerator.
根據所述一實施例,在銅鍍液中,第一整平劑的R1 作為包含氮的飽和雜環化合物,是吡咯烷、吡唑烷、噁唑烷、噻唑烷中的一種。第一整平劑的R2 和R3 單獨包含氫。第一整平劑的m為500至1000的整數,第一整平劑的X是鹵族元素中的一種。According to one embodiment, in the copper plating solution, as a saturated heterocyclic compound containing nitrogen, R 1 of the first leveler is one of pyrrolidine, pyrazolidine, oxazolidine, and thiazolidine. R 2 and R 3 of the first leveling agent contain hydrogen alone. The m of the first leveling agent is an integer of 500 to 1000, and X of the first leveling agent is one of halogen elements.
根據所述一實施例,銅鍍液中的第二整平劑的R4 和R6 單獨包含氫。第二整平劑的R5 是苯基或苯甲基中的一種。R7 包含含一個氮的氨基。整平劑的n為80至180的整數。According to one embodiment, R 4 and R 6 of the second leveler in the copper plating solution contain hydrogen alone. R 5 of the second leveler is one of phenyl or benzyl. R 7 contains an amino group containing one nitrogen. The n of the leveling agent is an integer of 80 to 180.
與所述一實施例相同地,使用光學顯微鏡及雷射掃描共聚焦顯微鏡,對作為比較例製得的鍍品進行分析。In the same manner as in the above-mentioned Example, a plated product prepared as a comparative example was analyzed using an optical microscope and a laser scanning confocal microscope.
圖5是本發明的一比較例的銅電鍍之後使用光學顯微鏡觀測到的圖。FIG. 5 is a diagram observed with an optical microscope after copper plating according to a comparative example of the present invention.
圖6是本發明的一比較例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的三維掃描圖。FIG. 6 is a three-dimensional scanning view of a comparative example of the present invention, which was measured using a laser scanning confocal microscope after copper plating.
圖7是本發明的一比較例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的輪廓結果。FIG. 7 is a profile result measured using a laser scanning confocal microscope after copper plating according to a comparative example of the present invention.
參照圖5至圖7,在不浸漬於前處理溶液而直接進行電鍍時,測得布線內厚度的不均勻度為14.1%。Referring to FIGS. 5 to 7, when the plating was performed directly without being immersed in the pretreatment solution, the unevenness of the thickness in the wiring was measured to be 14.1%.
確認到根據本發明一實施例實驗時布線內厚度的不均勻度為2.5%,這與比較例的實驗結果即14.1%相比改善了11.6%。It was confirmed that the unevenness of the thickness in the wiring during the experiment according to an example of the present invention was 2.5%, which was an 11.6% improvement over the experimental result of the comparative example, which was 14.1%.
這是因為在電鍍之前,藉由前處理溶液的浸漬,預先吸附了第一整平劑。在根據本發明一實施例實施前處理的情況下,由於在電鍍之前第一整平劑已吸附於基板,發揮介面活性化及引導鍍液浸透至布線內的作用,從而在電鍍時,將鍍液內的電解液均勻供給至基板的表面,能夠產生高平整度效果。This is because the first leveling agent was adsorbed in advance by the immersion of the pretreatment solution before plating. In the case of performing the pretreatment according to an embodiment of the present invention, since the first leveling agent has been adsorbed on the substrate before electroplating, it plays a role of activating the interface and guiding the plating solution to penetrate into the wiring. The electrolytic solution in the plating solution is uniformly supplied to the surface of the substrate, and a high flatness effect can be produced.
由此可知,如果根據本發明一實施例來形成銅鍍膜,則能夠製得具有高平整度的銅鍍膜。It can be seen that if a copper plating film is formed according to an embodiment of the present invention, a copper plating film with high flatness can be obtained.
對銅電鍍品進行說明,特徵在於,所述銅電鍍品根據本發明一實施例的所述銅電鍍方法製得。The copper electroplated product is described, characterized in that the copper electroplated product is made according to the copper electroplating method according to an embodiment of the present invention.
此時,所述銅電鍍品的特徵在於,在電鍍前,先將基板浸漬於前處理溶液中。At this time, the copper electroplated product is characterized in that the substrate is immersed in a pretreatment solution before electroplating.
例如,所述銅電鍍品可包括具有銅布線的電路基板或具有銅布線的半導體。For example, the copper plating product may include a circuit substrate having a copper wiring or a semiconductor having a copper wiring.
就本發明一實施例的銅電鍍品而言,由於電鍍前先浸漬於前處理溶液中,因此預先吸附了第一整平劑,從而能夠得到具有高平整度銅鍍膜的鍍品。In the copper electroplated product according to an embodiment of the present invention, the first leveling agent is adsorbed in advance because the copper electroplated product is immersed in the pre-treatment solution before electroplating, so that a plated product having a high flatness copper plating film can be obtained.
如前所述的本發明的說明用於例示,本案所屬技術領域中具有通常知識者可理解不變更本發明的技術思想或必要技術特徵的前提下,可容易地變更為其他具體的方式。因此,應理解如上所述的多個實施例在所有方面進行例示,而並非限定。例如,以單一型說明的各技術特徵可以分散實施,同樣也可以將分散說明的技術特徵以結合的方式實施。As described above, the description of the present invention is for illustration, and a person having ordinary knowledge in the technical field to which this case pertains can easily change to other specific methods without comprehending the technical idea or necessary technical features of the present invention. Therefore, it should be understood that the various embodiments described above are exemplified in all aspects and are not limited. For example, the technical features described in a single type may be implemented in a decentralized manner, and the technical features described in a decentralized manner may also be implemented in a combined manner.
本發明的範圍由後述的申請專利範圍表示,應解釋為從申請專利範圍的意義、範圍及其等同概念匯出的所有變更或變形的方式均包含在本發明的範圍內。The scope of the present invention is indicated by the scope of patent application to be described later, and it should be construed that all changes or modifications derived from the meaning, scope and equivalent concept of the scope of patent application are included in the scope of the invention.
S100~S300‧‧‧步驟S100 ~ S300‧‧‧step
圖1是表示本發明一實施例的銅電鍍方法的流程圖。FIG. 1 is a flowchart showing a copper plating method according to an embodiment of the present invention.
圖2是本發明一實施例的銅電鍍之後使用光學顯微鏡觀測到的圖。FIG. 2 is a diagram observed with an optical microscope after copper plating according to an embodiment of the present invention.
圖3是本發明一實施例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的三維掃描圖。FIG. 3 is a three-dimensional scanning image measured by a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.
圖4是本發明一實施例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的輪廓(Profile)結果。FIG. 4 is a profile result measured using a laser scanning confocal microscope after copper plating according to an embodiment of the present invention.
圖5是本發明一比較例的銅電鍍之後使用光學顯微鏡觀測到的圖。FIG. 5 is a diagram observed with an optical microscope after copper plating in a comparative example of the present invention.
圖6是本發明一比較例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的三維掃描圖。FIG. 6 is a three-dimensional scanning diagram measured by a laser scanning confocal microscope after copper plating of a comparative example of the present invention.
圖7是本發明一比較例的銅電鍍之後使用雷射掃描共聚焦顯微鏡測定的輪廓結果。FIG. 7 is a profile result measured using a laser scanning confocal microscope after copper plating in a comparative example of the present invention.
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