WO2020042230A1 - 一种高寿命铜钼蚀刻液及蚀刻方法 - Google Patents

一种高寿命铜钼蚀刻液及蚀刻方法 Download PDF

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Publication number
WO2020042230A1
WO2020042230A1 PCT/CN2018/105401 CN2018105401W WO2020042230A1 WO 2020042230 A1 WO2020042230 A1 WO 2020042230A1 CN 2018105401 W CN2018105401 W CN 2018105401W WO 2020042230 A1 WO2020042230 A1 WO 2020042230A1
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etching solution
copper
etching
molybdenum
mother liquid
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French (fr)
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赵芬利
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/44Compositions for etching metallic material from a metallic material substrate of different composition
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • C23F1/18Acidic compositions for etching copper or alloys thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • C23F1/26Acidic compositions for etching refractory metals

Definitions

  • the present application provides a high-lifetime copper-molybdenum etching solution, including: an etching solution mother liquid and an etching solution sub-liquid; the main components of the etching solution mother liquid include 10 to 20% of hydrogen peroxide in the total mass percentage of the etching solution mother liquid Regulators that account for 1 to 10% of the total mass of the etching solution mother liquid, stabilizers that account for 0.5 to 5% of the total mass of the etching solution mother liquid, and 1 to 10 for the total mass of the etching solution mother liquid % Organic acid, 0.001 to 1% inhibitor of the total mass of the etching solution mother liquid, and pH adjuster 1 to 10% of the total mass of the etching solution mother liquid, the balance is deionized water;
  • the main components of the etching solution sub-liquid include a dissolving agent which accounts for 3 to 10% by mass relative to the etching solution mother liquid, and the organic acid which accounts for 0.05 to 0.5% by mass relative to the etching solution mother solution.
  • the stabilizer is phenylurea.
  • the present application also provides a method for etching a copper-molybdenum metal film layer using the high-lifetime copper-molybdenum etching solution, including:
  • the copper ion concentration dissolved in the etching solution mother liquid during the etching process is zero as a starting point, and the etch solution mother liquid is added dropwise to the etching solution mother liquid every time when the increase is 0.001 g per milliliter, until completion The patterning process of the copper-molybdenum metal film layer.
  • an etching temperature of the etching solution ranges from 30 to 35 ° C.
  • the beneficial effect of the present application is that the high-life copper-molybdenum etching solution and etching method provided by the present application, by adding a composition of a dissolving agent, an organic acid, an inhibitor, and a stabilizer to the etching solution with a certain copper ion concentration, further The service life of the etching solution is extended, and the stability of the etching quality is further improved.
  • FIG. 1 is a flowchart of an etching method for a copper-molybdenum metal film layer of the present application.
  • FIG. 2 is a schematic view of a scanning electron microscope after etching a copper-molybdenum metal film layer of the present application.
  • This application is directed to the existing copper-molybdenum etching solution and etching method.
  • concentration of copper ions dissolved in the etching solution during the etching process exceeds 0.005 g per milliliter, the etching efficiency is low, which further causes the etching quality to be low and needs to be replaced.
  • the technical problem of the new etching solution, this embodiment can solve this defect.
  • the hydrogen peroxide in the etching solution mother liquid functions as an oxidant and oxidizes copper and molybdenum.
  • the content of the hydrogen peroxide in the etching solution mother liquid is preferably 10% to 20% of the total mass of the etching solution mother liquid. . Within this range, the oxidation ability is ensured, and the etching speed is not too fast, making it difficult to control the etching process.
  • the regulator is used to stabilize hydrogen peroxide, inhibit its decomposition, ensure the safety of operation, and extend the life of the etching solution.
  • the content of the regulator may be preferably 1 to 10% of the total mass of the etching solution mother liquid, which is an amine compound; the amine compound is selected from 2-amino-2-methyl-1-propanol, At least one of methylamine, diethylamine, N-ethylbenzylamine, N, N-dimethylcyclohexylamine, N-methyl-N-cyclohexylbenzylamine, and acetanilide.
  • the role of the stabilizer is to stabilize hydrogen peroxide.
  • the content of the stabilizer may preferably be 0.5 to 5% of the total mass of the etching solution mother liquid; the stabilizer is phenylurea.
  • the organic acid is used for etching copper-molybdenum alloy as long as the composition can adjust the etching speed.
  • the specific acid can also be used as a masking agent for metal ions after etching to suppress the decomposition rate of hydrogen peroxide; the organic acid
  • the content may preferably be 1 to 10% of the total mass of the etching solution mother liquid. If it is less than 1% by weight, the etching rate is slowed down, and etching cannot be achieved within a controlled engineering time.
  • the inhibitor is for controlling the etching speed and the bevel.
  • the content of the inhibitor may preferably be 0.001 to 1% of the total mass of the etching solution mother liquid; within this range, the angle of the oblique angle can be effectively controlled between 25-60 ° without slowing down Etching speed.
  • the inhibitor is selected from at least one of 2-aminothiazole, 2-amino-5-nitrothiazole, 3-amino-1,2,4-triazole, benzotriazole, and sodium triazole nitrogen.
  • the dissolving agent is mainly used to better dissolve the etching solution mother liquid, copper ions, and other components of the etching solution sub-liquid together to improve the etching efficiency.
  • the content of the dissolving agent may be preferably 3 to 10% by mass relative to the etching solution mother liquid; the dissolving agent is selected from at least one of ethyl acetate, acetonitrile, and tetrahydrofuran.
  • the high-lifetime copper-molybdenum etching solution of the present application includes an etching solution mother liquid and an etching solution sub-liquid, wherein the etching solution mother liquid is preferably an etching solution A, and the etching solution A includes 15% of peroxide in a total mass percentage of the etching solution.
  • the etching solution sub-liquid is preferably an etching solution B.
  • the etching solution B includes ethyl ester which accounts for 5% by mass relative to the etching solution A and lemon which accounts for 0.2% by mass relative to the etching solution A. Acid, 0.1% of glycolic acid relative to the mass of the etching solution A, benzotriazole of 0.005% of the mass relative to the solution of the etchant A, and 0.05% phenylurea.
  • the present application further provides a method flow for etching a copper-molybdenum metal film layer using the high-lifetime copper-molybdenum etching solution.
  • the method includes:
  • the S10 further includes:
  • a substrate is provided, and a metal layer is formed by etching on the surface of the substrate using a physical weather deposition method;
  • the substrate is, for example, a glass substrate; in some embodiments, the substrate may also be a composite film layer, which may include passivation Layer, metal oxide semiconductor layer (such as indium gallium zinc oxide layer), amorphous phase silicon layer and / or silicon nitride layer, or other suitable materials, but is not limited thereto.
  • the metal layer includes a molybdenum layer and a copper layer. The molybdenum layer can be formed on the substrate first, and then the copper layer can be formed on the molybdenum layer to finally obtain a copper-molybdenum metal film layer.
  • the molybdenum metal film layer is removed, and an unnecessary portion of the copper molybdenum metal film layer is removed, and the concentration of copper ions dissolved in the etching solution A during the etching process is measured.
  • the S30 further includes:
  • the instrument is used to record the concentration of copper ions dissolved in the etching solution A during the etching process.
  • concentration of copper ions dissolved in the etching solution A increases by 0.001 grams per milliliter, it is dropped into the etching solution mother liquid.
  • Add the etching solution B and continue to etch the copper-molybdenum metal layer after mixing.
  • concentration of copper ions dissolved in the etching solution A reaches 0.012 grams per milliliter, it is observed that the mixed solution does not bump. Repeat the above steps until the patterning process of the copper-molybdenum metal film layer is completed.
  • the scanning copper microscope observed the copper-molybdenum metal film layer as shown in FIG. 2, where the etching cone angle is 43.4 °, and after the copper-molybdenum metal film layer is etched, the etching cone angle reaches the edge size of the copper-molybdenum metal film layer The length is 790 nanometers.
  • the copper-molybdenum metal film layer is less than or equal to 60 degrees, which indicates that the copper-molybdenum metal film layer has relatively smooth sides, which is conducive to subsequent formation of other film layers on the copper-molybdenum metal film layer, which is not easy to be subsequently formed. Fracture or rupture of the film.
  • the stability of the etching quality can be ensured and the molybdenum ion remains. Does not change due to the increase in copper ion concentration, and at the same time increases the service life of the etching solution. When the copper ion reaches 0.012 grams per milliliter, it will not cause bumping of the solution and maintain a stable etching effect.
  • the high-life copper and molybdenum etching solution and etching method provided by the present application are further extended by adding a composition of a dissolving agent, an organic acid, an inhibitor, and a stabilizer to an etching solution having a certain copper ion concentration.
  • the service life of the etching solution further improves the stability of the etching quality.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

一种高寿命铜钼蚀刻液,包括:蚀刻液母液以及蚀刻液子液;所述蚀刻液母液的主要成分包括过氧化氢、调节剂、稳定剂、有机酸、抑制剂以及pH调节剂,余量为去离子水;所述蚀刻液子液的主要成分包括溶解剂、所述有机酸、所述抑制剂以及所述稳定剂。还提供一种用于铜钼金属膜层的蚀刻方法。

Description

一种高寿命铜钼蚀刻液及蚀刻方法 技术领域
本申请涉及铜制程刻蚀领域,尤其涉及一种高寿命铜钼蚀刻液及蚀刻方法。
背景技术
目前随着显示器尺寸的增大,栅极及数据金属配线通常使用铜金属;这是因为相较于铝金属,铜的电阻值低,加工性能优异;铜导线线宽不需要达到铝导线的宽度,可以节省溅镀靶材的材料成本,提高液晶显示器的穿透度与背光源使用效率,更加适合高分辨率面板的制作。钼具有与玻璃等基板的密合性高、难以产生向硅半导体膜的扩散、且兼具阻挡性;因此,将包含铜、以铜为主成分的铜钼合金的层叠膜通过溅射法等成膜工艺在玻璃等基板上成膜,然后经过将抗蚀剂等作为掩膜进行蚀刻的蚀刻工序而成为电极图案。
现有的铜钼蚀刻液及蚀刻方法,为了提高蚀刻铜钼合金的速度,常常加入氟化物。添加氟化物的蚀刻液容易腐蚀玻璃,对器件有腐蚀;而且刻蚀效率低,稳定性差。当刻蚀过程中溶解在蚀刻液中的铜离子浓度超过0.005克每毫升时,为了保证蚀刻品质,需要更换新的蚀刻液。因此,亟需一种环境友好、生产安全、加工精度高,且易于控制的蚀刻液。
综上所述,现有的铜钼蚀刻液及蚀刻方法,由于刻蚀过程中溶解在蚀刻液中的铜离子浓度超过0.005克每毫升时,导致刻蚀效率低,进一步造成刻蚀品质低下,需要更换新的蚀刻液。
技术问题
现有的铜钼蚀刻液及蚀刻方法,当刻蚀过程中溶解在蚀刻液中的铜离子浓度超过0.005克每毫升时,导致刻蚀效率低,进一步造成刻蚀品质低下,需要更换新的蚀刻液。
技术解决方案
本申请提供一种高寿命铜钼蚀刻液及蚀刻方法,能够延长蚀刻液的使用寿命,以解决现有的铜钼蚀刻液及蚀刻方法,由于刻蚀过程中溶解在蚀刻液中的铜离子浓度超过0.005克每毫升时,导致刻蚀效率低,进一步造成刻蚀品质低下,需要更换新的蚀刻液的技术问题。
为解决上述问题,本申请提供的技术方案如下:
本申请提供一种高寿命铜钼蚀刻液,包括:蚀刻液母液以及蚀刻液子液;所述蚀刻液母液的主要成分包括占所述蚀刻液母液总质量百分比为10~20%的过氧化氢、占所述蚀刻液母液总质量百分比为1~10%的调节剂、占所述蚀刻液母液总质量百分比为0.5~5%的稳定剂、占所述蚀刻液母液总质量百分比为1~10%的有机酸、占所述蚀刻液母液总质量百分比为0.001~1%的抑制剂以及占所述蚀刻液母液总质量百分比为1~10%的pH调节剂,余量为去离子水;所述蚀刻液子液的主要成分包括占相对于所述蚀刻液母液质量百分比为3~10%的溶解剂、占相对于所述蚀刻液母液质量百分比为0.05~0.5%的所述有机酸、占相对于所述蚀刻液母液质量百分比为0.001~0.01%的所述抑制剂以及占相对于所述蚀刻液母液质量百分比为0.01~0.1%的所述稳定剂。
在本申请实施例所提供的高寿命铜钼蚀刻液中申请,所述调节剂为胺类化合物。
在本申请实施例所提供的高寿命铜钼蚀刻液中申请,所述胺类化合物选自2-氨基-2-甲基-1-丙醇、甲胺、二乙胺、N-乙基苄基胺、N,N-二甲基环己胺、N-甲基-N-环己苄基胺以及乙酰苯胺中的至少一种。
在本申请实施例所提供的高寿命铜钼蚀刻液中申请,所述稳定剂为苯基脲。
在本申请实施例所提供的高寿命铜钼蚀刻液中申请,所述有机酸选自乙醇酸、柠檬酸、2,3-二羟基丁二酸、2-羟基丁二酸、2-羟基丙酸以及邻苯二甲酸中的至少一种。
在本申请实施例所提供的高寿命铜钼蚀刻液中申请,所述抑制剂选自2-氨基噻唑、2-氨基-5-硝基噻唑、3-氨基-1,2,4-三唑、苯并三唑以及三唑氮钠中的至少一种。
在本申请实施例所提供的高寿命铜钼蚀刻液中申请,所述pH调节剂选自磷酸氢二铵、碳酸钠、乙酸钠、磷酸钠以及碳酸氢钠中的至少一种。
在本申请实施例所提供的高寿命铜钼蚀刻液中申请,所述溶解剂选自乙酯、乙腈以及四氢呋喃中的至少一种。
本申请还提供一种使用所述高寿命铜钼蚀刻液蚀刻铜钼金属膜层的方法,包括:
S10,提供一基板,形成一铜钼金属膜层于所述基板上;
S20,使用所述蚀刻液母液对所述铜钼金属膜层进行刻蚀;
S30,以刻蚀过程中溶解在所述蚀刻液母液中的铜离子浓度零为起始点,每增加0.001克每毫升时,向所述蚀刻液母液中滴加所述蚀刻液子液,直到完成所述铜钼金属膜层的图案化制程。
在本申请实施例所提供的使用所述高寿命铜钼蚀刻液蚀刻铜钼金属膜层的方法中申请,所述蚀刻液的蚀刻温度的范围为30~35℃。
有益效果
本申请的有益效果为:本申请申请所提供的高寿命铜钼蚀刻液及蚀刻方法,通过向一定铜离子浓度的蚀刻溶液中加入溶解剂、有机酸、抑制剂以及稳定剂的组合物,进一步延长了蚀刻液的使用寿命,更进一步提高了蚀刻品质的稳定性。
附图说明
为了更清楚地说明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单介绍,显而易见地,下面描述中的附图仅仅是申请的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本申请用于铜钼金属膜层的蚀刻方法流程图。
图2为本申请铜钼金属膜层蚀刻后扫描电镜示意图。
本发明的最佳实施方式
以下各实施例的说明是参考附加的图示,用以例示本申请可用以实施的特定实施例。本申请所提到的方向用语,例如[上]、[下]、[前]、[后]、[左]、[右]、[内]、[外]、[侧面]等,仅是参考附加图式的方向。因此,使用的方向用语是用以说明及理解本申请,而非用以限制本申请。在图中,结构相似的单元是用以相同标号表示。
本申请针对现有的铜钼蚀刻液及蚀刻方法,由于刻蚀过程中溶解在蚀刻液中的铜离子浓度超过0.005克每毫升时,导致刻蚀效率低,进一步造成刻蚀品质低下,需要更换新的蚀刻液的技术问题,本实施例能够解决该缺陷。
本申请提供一种高寿命铜钼蚀刻液,包括:蚀刻液母液以及蚀刻液子液;所述蚀刻液母液的主要成分包括占所述蚀刻液母液总质量百分比为10~20%的过氧化氢、占所述蚀刻液母液总质量百分比为1~10%的调节剂、占所述蚀刻液母液总质量百分比为0.5~5%的稳定剂、占所述蚀刻液母液总质量百分比为1~10%的有机酸、占所述蚀刻液母液总质量百分比为0.001~1%的抑制剂以及占所述蚀刻液母液总质量百分比为1~10%的pH调节剂,余量为去离子水;所述蚀刻液子液的主要成分包括占相对于所述蚀刻液母液质量百分比为3~10%的溶解剂、占相对于所述蚀刻液母液质量百分比为0.05~0.5%的所述有机酸、占相对于所述蚀刻液母液质量百分比为0.001~0.01%的所述抑制剂以及占相对于所述蚀刻液母液质量百分比为0.01~0.1%的所述稳定剂。
其中,所述蚀刻液母液中的过氧化氢是作为氧化剂的功能,将铜和钼氧化,该蚀刻液母液中过氧化氢的含量优选为占所述蚀刻液母液总质量百分比为10~20%。在此范围内,既确保了氧化能力,又不至于腐蚀速度过快,难以控制蚀刻工艺。
所述调节剂是用以稳定过氧化氢,抑制其分解,保障操作安全性、延长所述蚀刻液寿命。所述调节剂的含量可优选为占所述蚀刻液母液总质量百分比为1~10%,为胺类化合物;所述胺类化合物选自2-氨基-2-甲基-1-丙醇、甲胺、二乙胺、N-乙基苄基胺、N,N-二甲基环己胺、N-甲基-N-环己苄基胺以及乙酰苯胺中的至少一种。
所述稳定剂的作用是稳定过氧化氢。所述稳定剂的含量可优选为占所述蚀刻液母液总质量百分比为0.5~5%;所述稳定剂为苯基脲。
所述有机酸是用于蚀刻铜钼合金的只要成分,可调节蚀刻速度,另外,特定的酸在蚀刻完之后还可作为金属离子的掩蔽剂来抑制过氧化氢分解的速率;所述有机酸的含量可优选为占所述蚀刻液母液总质量百分比为1~10%,若其不足1%重量百分比时,蚀刻速度变慢,在可控制的工程时间内无法实现蚀刻,若其超出10%重量百分比时,蚀刻速度过快,难以控制工程进展;所述有机酸选自乙醇酸、柠檬酸、2,3-二羟基丁二酸、2-羟基丁二酸、2-羟基丙酸以及邻苯二甲酸中的至少一种。
所述抑制剂是为了控制蚀刻速度和斜角。所述抑制剂的含量可优选为占所述蚀刻液母液总质量百分比为0.001~1%;在此范围内,既能有效控制斜角的角度在25-60°之间,又不至于拖慢蚀刻速度。所述抑制剂选自2-氨基噻唑、2-氨基-5-硝基噻唑、3-氨基-1,2,4-三唑、苯并三唑以及三唑氮钠中的至少一种。
所述pH调节剂主要是为了调节所述所述蚀刻液母液中的pH值。所述蚀刻液母液中的pH值过小,蚀刻能力太强,容易将铜镍层都蚀刻干净;所述蚀刻液母液中的pH值过大,过氧化氢稳定性会降低,缩短蚀刻液寿命;所述pH调节剂的含量可优选为占所述蚀刻液母液总质量百分比为1~10%;所述pH调节剂选自磷酸氢二铵、碳酸钠、乙酸钠、磷酸钠以及碳酸氢钠中的至少一种。
所述溶解剂主要是为了使所述蚀刻液母液、铜离子以及所述蚀刻液子液的其他成分更好的溶解在一起,提升蚀刻效率。所述溶解剂的含量可优选为占相对于所述蚀刻液母液质量百分比为3~10%;所述溶解剂选自乙酯、乙腈以及四氢呋喃中的至少一种。
本申请提供的高寿命铜钼蚀刻液的制备方法简单,只需在室温下将相应重量份的组分混合均匀即可。
同时,本申请中采用过氧化氢做氧化剂,不含有氟化物,氧化性强,且又绿色环保,能很好的氧化铜跟钼,再配以所述缓冲溶液,能更好的去除源自铜跟钼的残渣,有助于蚀刻。但由于过氧化氢的低对称性以及过氧键的存在,造成了过氧化氢的自分解,特别是过氧化氢含量高及某些金属离子存在时,很容易发生“暴沸”现象,为了保障操作安全性及保障蚀刻效果,辅以所述抑制剂来抑制过氧化氢分解,控制蚀刻速度和斜角,减小侧蚀,避免底切,使蚀刻后的布线截面形状良好。
本申请高寿命铜钼蚀刻液包括蚀刻液母液以及蚀刻液子液,其中所述蚀刻液母液优选为蚀刻液A,所述蚀刻液A包括占所述蚀刻液总质量百分比为15%的过氧化氢、占所述蚀刻液A总质量百分比为4.5%的2-氨基-2-甲基-1-丙醇、占所述蚀刻液A总质量百分比为2.5%的苯基脲、占所述蚀刻液A总质量百分比为5%的柠檬酸、占所述蚀刻液A总质量百分比为2.5%的苯甲酸、占所述蚀刻液A总质量百分比为0.1%的苯并三唑、占所述蚀刻液A总质量百分比为3%的磷酸氢二铵,余量为占所述蚀刻液A总质量百分比为74%去离子水。
所述蚀刻液子液优选为蚀刻液B,所述蚀刻液B包括占相对于所述蚀刻液A质量百分比为5%的乙酯、占相对于所述蚀刻液A质量百分比为0.2%的柠檬酸、占相对于所述蚀刻液A质量百分比为0.1%的乙醇酸、占相对于所述蚀刻液A质量百分比为0.005%的苯并三氮唑以及占相对于所述蚀刻液A质量百分比为0.05%的苯基脲。
如图1所示,本申请还提供使用所述高寿命铜钼蚀刻液蚀刻铜钼金属膜层的方法流程,所述方法包括:
S10,提供一基板,形成一铜钼金属膜层于所述基板上;
具体的,所述S10还包括:
首先,提供一基板,利用物理气象沉积法在所述基板表面刻蚀形成一金属层;所述基板例如是玻璃基板;一些实施例中,所述基板也可以是复合膜层,可包括钝化层、金属氧化物半导体层(例如氧化铟镓锌层)、非晶相硅层和/或氮化硅层、或其他适合的材质,但不限于此。所述金属层包括一钼层以及一铜层,可先形成所述钼层于所述基板上,然后再形成所述铜层于所述钼层上,最终得到铜钼金属膜层。所述钼层的作用为增加所述铜层与所述基板的贴附性,阻挡所述铜层向所述基板扩散。所述钼层的厚度优选为100~400埃米,所述铜层的厚度优选为2500~10000埃米。
S20,使用所述蚀刻液母液对所述铜钼金属膜层进行刻蚀。
具体的,所述S20还包括:
首先设置一光阻层于所述金属层的表面,之后以所述光阻层为掩膜,使用配置好的所述蚀刻液A在蚀刻温度的范围为30~35℃之间蚀刻所述铜钼金属膜层,并去除不需要部分的铜钼金属膜层,测量蚀刻过程中溶解在所述蚀刻液A中的铜离子浓度。
S30,以刻蚀过程中溶解在所述蚀刻液母液中的铜离子浓度零为起始点,每增加0.001克每毫升时,向所述蚀刻液母液中滴加所述蚀刻液子液,直到完成所述铜钼金属膜层的图案化制程。
具体的,所述S30还包括:
首先使用仪器时刻记录蚀刻过程中溶解在所述蚀刻液A中的铜离子浓度,当溶解在所述蚀刻液A中的铜离子浓度每增加0.001克每毫升时,向所述蚀刻液母液中滴加所述蚀刻液B,混合均匀后继续刻蚀所述铜钼金属层;当溶解在所述蚀刻液A中的铜离子浓度达到0.012克每毫升时,观察到上述混合溶液没有出现突沸现象,重复以上直到完成所述铜钼金属膜层的图案化制程。
蚀刻制程后,所述铜钼金属膜层蚀刻后的蚀刻锥角小于或等于60度,所述铜钼金属膜层蚀刻后的边缘尺寸长度范围为600~1200纳米。
通过扫描电镜观测到所述铜钼金属膜层如图2所示,其中蚀刻锥角为43.4°,所述铜钼金属膜层蚀刻后,所述蚀刻锥角到铜钼金属膜层的边缘尺寸长度为790纳米。所述铜钼金属膜层小于或等于60度代表所述铜钼金属膜层具有相对平缓的侧边,有利于后续形成其他膜层于所述铜钼金属膜层上时,不易发生后续形成的膜层的断裂或破裂情形。
本申请用于铜钼金属膜层的蚀刻方法中,通过向一定铜离子浓度的蚀刻溶液中加入溶解剂、有机酸、抑制剂以及稳定剂的组合物,可以保证蚀刻品质的稳定,钼离子残留不会因为铜离子浓度的增加而变化,同时增加了蚀刻液的使用寿命。当铜离子达到0.012克每毫升的时候不会引起溶液的突沸,并保持稳定的蚀刻效果。
本申请的有益效果:本申请所提供的高寿命铜钼蚀刻液及蚀刻方法,通过向一定铜离子浓度的蚀刻溶液中加入溶解剂、有机酸、抑制剂以及稳定剂的组合物,进一步延长了蚀刻液的使用寿命,更进一步提高了蚀刻品质的稳定性。
综上所述,虽然本申请已以优选实施例揭露如上,但上述优选实施例并非用以限制本申请,本领域的普通技术人员,在不脱离本申请的精神和范围内,均可作各种更动与润饰,因此本申请的保护范围以权利要求界定的范围为准。

Claims (10)

  1. 一种高寿命铜钼蚀刻液,其中,包括:蚀刻液母液以及蚀刻液子液;所述蚀刻液母液的主要成分包括占所述蚀刻液母液总质量百分比为10~20%的过氧化氢、占所述蚀刻液母液总质量百分比为1~10%的调节剂、占所述蚀刻液母液总质量百分比为0.5~5%的稳定剂、占所述蚀刻液母液总质量百分比为1~10%的有机酸、占所述蚀刻液母液总质量百分比为0.001~1%的抑制剂以及占所述蚀刻液母液总质量百分比为1~10%的pH调节剂,余量为去离子水;所述蚀刻液子液的主要成分包括占相对于所述蚀刻液母液质量百分比为3~10%的溶解剂、占相对于所述蚀刻液母液质量百分比为0.05~0.5%的所述有机酸、占相对于所述蚀刻液母液质量百分比为0.001~0.01%的所述抑制剂以及占相对于所述蚀刻液母液质量百分比为0.01~0.1%的所述稳定剂。
  2. 根据权利要求1所述的高寿命铜钼蚀刻液,其中,所述调节剂为胺类化合物。
  3. 根据权利要求2所述的高寿命铜钼蚀刻液,其中,所述胺类化合物选自2-氨基-2-甲基-1-丙醇、甲胺、二乙胺、N-乙基苄基胺、N,N-二甲基环己胺、N-甲基-N-环己苄基胺以及乙酰苯胺中的至少一种。
  4. 根据权利要求1所述的高寿命铜钼蚀刻液,其中,所述稳定剂为苯基脲。
  5. 根据权利要求1所述的高寿命铜钼蚀刻液,其中,所述有机酸选自乙醇酸、柠檬酸、2,3-二羟基丁二酸、2-羟基丁二酸、2-羟基丙酸以及邻苯二甲酸中的至少一种。
  6. 根据权利要求1所述的高寿命铜钼蚀刻液,其中,所述抑制剂选自2-氨基噻唑、2-氨基-5-硝基噻唑、3-氨基-1,2,4-三唑、苯并三唑以及三唑氮钠中的至少一种。
  7. 根据权利要求1所述的高寿命铜钼蚀刻液,其中,所述pH调节剂选自磷酸氢二铵、碳酸钠、乙酸钠、磷酸钠以及碳酸氢钠中的至少一种。
  8. 根据权利要求1所述的高寿命铜钼蚀刻液,其中,所述溶解剂选自乙酯、乙腈以及四氢呋喃中的至少一种。
  9. 一种使用如权利要求1所述的高寿命铜钼蚀刻液蚀刻铜钼金属膜层的方法,其中,包括:
    S10,提供一基板,形成一铜钼金属膜层于所述基板上;
    S20,使用所述蚀刻液母液对所述铜钼金属膜层进行刻蚀;
    S30,以刻蚀过程中溶解在所述蚀刻液母液中的铜离子浓度零为起始点,每增加0.001克每毫升时,向所述蚀刻液母液中滴加所述蚀刻液子液,直到完成所述铜钼金属膜层的图案化制程。
  10. 根据权利要求9所述的高寿命铜钼蚀刻液蚀刻铜钼金属膜层的方法,其中,所述蚀刻液的蚀刻温度的范围为30~35℃。
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