Cleaning method for semiconductor device, cleaning equipment for semiconductor device and composition for semiconductor cleaning

Abstract

To provide a cleaning method for a semiconductor device, cleaning equipment for the semiconductor device and a composition for semiconductor cleaning.SOLUTION: A cleaning method for a semiconductor device includes steps of: providing a composition for semiconductor cleaning, containing a mixture and hydrogen peroxide; and bringing the composition for semiconductor cleaning into contact with a semiconductor device to clean the semiconductor device. The semiconductor device includes a titanium composition and an aluminum composition, and the mixture contains ammonium hydroxide, an organic solvent, and an etching inhibitor for an etching stop layer. A weight ratio of the ammonium hydroxide and the etching inhibitor for the etching stop layer is 1:1-20:1. An etching rate of the composition for semiconductor cleaning with respect to the titanium component is 170 Å / min or more. An etching rate of the composition for semiconductor cleaning with respect to the aluminum component is 1 Å / min or less. Thus, an efficiency for removing residues and titanium components after etching can be improved, and corrosiveness to metal leads, a dielectric layer and the etching stop layer can be reduced.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a method for cleaning a semiconductor device, a semiconductor device cleaning equipment, and a semiconductor cleaning composition, and more particularly to a method for cleaning a semiconductor device, a semiconductor device cleaning equipment, and a semiconductor cleaning composition that can remove post-etching residues and titanium-containing compounds. [Background technology]

[0002] During the manufacturing process of semiconductor or microelectronic devices, patterning of semiconductor or dielectric layers is often achieved through multiple photoresist shielding and dry etching processes. Dry etching generates post-etch residues in semiconductor vias or channels. These residues include fluorocarbon polymers (CFx polymers) and metal fluorides, and appropriate cleaning compositions are required to remove the residues. To simplify subsequent manufacturing processes, removing the residues may also require the removal of hard masks made of titanium-containing compounds, such as titanium nitride. In this case, the cleaning composition must also have the ability to remove the titanium-containing compounds. Summary of the Invention [Problem to be solved by the invention]

[0003] However, in the process of removing titanium-containing compounds, problems such as reduced removal efficiency and corrosion of the metal leads (which may be materials such as copper, cobalt, aluminum, or tungsten), etch stop layers (which may be materials such as alumina or silicon carbide), and dielectric layers in the device occur, and the structure of the semiconductor or microelectronic device is destroyed. Therefore, conventional cleaning compositions cannot achieve rapid removal of titanium-containing compounds while avoiding corrosion of aluminum-containing compounds, so the cleaning effect is still not ideal. [Means for solving the problem]

[0004] An object of the present disclosure is to provide a method for cleaning a semiconductor device, a semiconductor device cleaning equipment, and a semiconductor cleaning composition that can remove post-etching residues and titanium-containing compounds from a semiconductor device and reduce corrosiveness to other structures.

[0005] According to one embodiment of one aspect of the present disclosure, there is provided a method for cleaning a semiconductor device, the method comprising the steps of: providing a semiconductor cleaning composition comprising a mixture and hydrogen peroxide; and contacting the semiconductor cleaning composition with the semiconductor device to clean the semiconductor device, wherein the semiconductor device comprises a titanium component comprising at least one of titanium metal and a titanium-containing compound, and an aluminum component comprising at least one of aluminum metal and an aluminum-containing compound, the mixture comprising ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor, the etch stop layer etch inhibitor being (1-hydroxy-1-phosphor-2-methyl-2-propanol). and a method for cleaning a semiconductor device, wherein the etching inhibitor is selected from the group consisting of ammonium hydroxide, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetrakis(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid), the weight ratio of ammonium hydroxide to the etching stop layer etch inhibitor is 1:1 to 20:1, and the etching rate of the semiconductor cleaning composition for titanium components is 170 Å / min or more, and the etching rate of the semiconductor cleaning composition for aluminum components is 1 Å / min or less.

[0006] According to the method for cleaning a semiconductor device, contacting the semiconductor cleaning composition with the semiconductor device may be by spraying the semiconductor cleaning composition onto the surface of the semiconductor device while the semiconductor device is rotating.

[0007] According to one embodiment of another aspect of the present disclosure, there is provided a semiconductor device cleaning equipment including: a cleaning composition delivery device for providing a semiconductor cleaning composition comprising a mixture and hydrogen peroxide; and a cleaning chamber communicating with the cleaning composition delivery device and accommodating a semiconductor device, wherein the semiconductor cleaning composition contacts the semiconductor device in the cleaning chamber to clean the semiconductor device, and the semiconductor device comprises a titanium component including at least one of titanium metal and a titanium-containing compound, and an aluminum component including at least one of aluminum metal and an aluminum-containing compound, the mixture comprising ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor, the etch stop layer etch inhibitor being selected from the group consisting of (1-hydroxy-1-phosphonoethyl)phosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetrakis(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid), and the weight ratio of the ammonium hydroxide to the etch stop layer etch inhibitor is 1:1 to 20:1.

[0008] According to the semiconductor device cleaning equipment, the cleaning chamber may include a rotating element on which the semiconductor device may be placed, and while the semiconductor device is rotating, the cleaning composition transport device can spray the semiconductor cleaning composition onto the surface of the semiconductor device.

[0009] According to one embodiment of another aspect of the present disclosure, there is provided a semiconductor cleaning composition comprising a mixture and hydrogen peroxide, wherein the mixture comprises ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor, the etch stop layer etch inhibitor being selected from the group consisting of (1-hydroxy-1-phosphonoethyl)phosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetrakis(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid), and the weight ratio of the ammonium hydroxide to the etch stop layer etch inhibitor is 1:1 to 20:1.

[0010] According to the semiconductor cleaning composition, the pH value of the mixture may be 6-10.

[0011] According to the semiconductor cleaning composition, the weight ratio of hydrogen peroxide in the semiconductor cleaning composition may be 10% to 25%, with the total weight of the semiconductor cleaning composition being 100%.

[0012] According to the semiconductor cleaning composition, the organic solvent may be selected from the group consisting of alcohol-based solvents, ether-based solvents, alcohol ether-based solvents, sulfone-based solvents, amide-based solvents, pyrrolidone-based solvents, and imidazolidinone-based solvents.

[0013] According to the semiconductor cleaning composition, the organic solvent may be methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol-t-butyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol-t-butyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene ...ethylene glycol ethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol t-butyl ether propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol monobutyl ether, propylene glycol-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol methyl butyl ether, dipropylene glycol monobutyl ether, 2,5,7,10-tetraoxaundecane, 4,7-dimethyl-2,5,9-trioxaundecane The alkyl acrylate may be selected from the group consisting of sadecane, 4-methyl-2,5,9-trioxadecane, tetrahydrofurfuryl alcohol, dimethyl sulfoxide, dimethyl sulfone, sulfolane, N,N-dimethylformamide, dimethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

[0014] According to the semiconductor cleaning composition, the mixture may further contain water, and the weight ratio of the organic solvent in the mixture may be 20% to 70% based on the total weight of the mixture being 100%.

[0015] According to the semiconductor cleaning composition, the mixture may further comprise a metal corrosion inhibitor.

[0016] According to the semiconductor cleaning composition, the metal corrosion inhibitor may be selected from the group consisting of benzotriazole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, 4-nitrobenzotriazole, 5-nitrobenzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, 1-phenylbenzotriazole, benzotriazole-4-carboxylic acid, benzotriazole-5-carboxylic acid, 4-aminobenzotriazole, 5-aminobenzotriazole, hydroxybenzotriazole, 2-(5-aminopentyl)benzotriazole, and 5-phenylthiol-benzotriazole.

[0017] According to the semiconductor cleaning composition, the mixture may further comprise a chelating agent.

[0018] According to the semiconductor cleaning composition, the chelating agent may be selected from the group consisting of glycine, alanine, cysteine, methionine, aspartic acid, asparagine, glutamic acid, glutamine, arginine, serine, histidine, iminodiacetic acid, nitrilotriacetic acid, N-(2-carboxyethyl)iminodiacetic acid, ethylenediaminetetraacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diaminetetraacetic acid, (S,S)-ethylenediamine-N,N'-disuccinic acid, hydroxyethylethylenediaminetriacetic acid, N,N-bis(2-hydroxyethyl)glycine, and dicarboxymethylglutamic acid. [Effects of the Invention]

[0019] Therefore, the present disclosure selects a specific type of compound as a component of the semiconductor cleaning composition and adjusts the ratio of ammonium hydroxide and etch stop layer etch inhibitor therein, thereby controlling the etching rate of the semiconductor cleaning composition for post-etching residues, titanium components, metal leads, dielectric layers and etch stop layers, thereby improving the efficiency of removing post-etching residues and titanium components and reducing the corrosiveness to metal leads, dielectric layers and etch stop layers. [Brief explanation of the drawings]

[0020] To make the above and other objects, features, advantages and embodiments of the present disclosure more clear and understandable, reference is made to the accompanying drawings as follows: [Figure 1] 1 is a process flowchart of a semiconductor device cleaning method according to an embodiment of the present disclosure. [Figure 2] FIG. 10 is a structural schematic diagram of a semiconductor device cleaning facility according to another embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0021] Each embodiment of the present disclosure will be discussed in more detail below. However, the embodiments may be applications of various disclosed concepts and may be specifically implemented within a variety of different specific scopes. The specific embodiments are for illustrative purposes only and are not intended to limit the scope of the disclosure. Furthermore, to simplify the drawings, some conventional structures and elements are simply illustrated in the drawings.

[0022] <Method for cleaning semiconductor device> Please refer to Fig. 1. Fig. 1 is a process flow chart of a semiconductor device cleaning method 100 according to one embodiment of the present disclosure. The semiconductor device cleaning method 100 includes steps 110 and 120.

[0023] Specifically, step 110 provides a semiconductor cleaning composition comprising a mixture of ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor, and hydrogen peroxide. The detailed formulation and proportion of the semiconductor cleaning composition will be described one by one in the following paragraphs, and therefore will not be described here.

[0024] Step 120 is to contact the semiconductor cleaning composition with the semiconductor device to clean the semiconductor device. The semiconductor device includes a titanium component including at least one of titanium metal and a titanium-containing compound, and an aluminum component including at least one of aluminum metal and an aluminum-containing compound. In step 120, the etching rate of the semiconductor cleaning composition for the titanium component is 170 Å / min or more, and the etching rate of the semiconductor cleaning composition for the aluminum component is 1 Å / min or less, thereby quickly removing the titanium component on the semiconductor device and reducing the etching resistance of the aluminum component.

[0025] The etching rate of the semiconductor cleaning composition for the titanium component may be 200 Å / min or more, or 250 Å / min or more, or 300 Å / min or more, or 350 Å / min or more, or 400 Å / min or more, or 450 Å / min or more but 500 Å / min or less. The etching rate of the semiconductor cleaning composition for the aluminum component may be 0.9 Å / min or less, or 0.8 Å / min or less, or 0.7 Å / min or less, or 0.6 Å / min or less, or 0.5 Å / min or less but 0.01 Å / min or more. This allows the etching rates of the semiconductor cleaning composition for the titanium component and the aluminum component to be adjusted to meet the needs of use.

[0026] In step 120, the semiconductor cleaning composition may be sprayed onto the surface of the semiconductor device while the semiconductor device is rotating, so that the semiconductor cleaning composition can be uniformly contacted with the semiconductor device, which can further improve the efficiency of removing titanium components from the surface. It should be noted that although the present disclosure takes the aforementioned spraying while rotating as an example, any manner in which the semiconductor cleaning composition can be contacted with the semiconductor device and achieve a cleaning effect (e.g., immersion, rinsing, or non-rotating spraying) should all fall within the scope of protection of the present disclosure.

[0027] <Semiconductor equipment cleaning equipment> Please refer to Figure 2, which is a structural schematic diagram of a semiconductor device cleaning equipment 200 according to another embodiment of the present disclosure. The semiconductor device cleaning equipment 200 includes a cleaning composition delivery device 210 and a cleaning chamber 220 that communicates with the cleaning composition delivery device 210 and that accommodates a semiconductor device (not shown).

[0028] Specifically, the cleaning composition delivery device 210 is used to provide a semiconductor cleaning composition containing a mixture of ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor, and hydrogen peroxide. The detailed formulation and proportion of the semiconductor cleaning composition will be described one by one in the following paragraphs, so a detailed description is omitted here.

[0029] The semiconductor cleaning composition contacts the semiconductor device in the cleaning chamber 220 to clean the semiconductor device, and the semiconductor device includes a titanium component including at least one of titanium metal and a titanium-containing compound, and an aluminum component including at least one of aluminum metal and an aluminum-containing compound. The components of the semiconductor cleaning composition can quickly remove the titanium component on the semiconductor device and reduce the etching sensitivity of the aluminum component.

[0030] The cleaning chamber 220 may include a rotating element 221 on which the semiconductor device may be placed, and while the semiconductor device is rotating, the cleaning composition delivery device 210 may spray the semiconductor cleaning composition onto the surface of the semiconductor device, thereby allowing the semiconductor cleaning composition to contact the semiconductor device more uniformly and further improving the efficiency of removing titanium components from the surface. It should be noted that although the present disclosure uses the rotating element 221 as an example, any structure or element that can bring the semiconductor cleaning composition into contact with the semiconductor device and achieve a cleaning effect (e.g., a tank body in which the semiconductor device can be immersed in the semiconductor cleaning composition, or a structure such as a non-rotating platform on which the semiconductor device can be placed) should all fall within the scope of protection of the present disclosure.

[0031] <Semiconductor cleaning composition> According to another embodiment of the present disclosure, there is provided a semiconductor cleaning composition comprising a mixture comprising ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor, and hydrogen peroxide. The etching stop layer etching inhibitor is a phosphonic acid compound and is selected from the group consisting of (1-hydroxy-1-phosphonoethyl)phosphonic acid (HEDP), nitrilotrimethylenetris(phosphonic acid) (NTMP), ethylenediaminetetra(methylenephosphonic acid) ({ethane-1,2-diylbis[nitrilobis(methylene)]}tetrakis(phosphonic acid) (EDTMP), hexamethylenediaminetetrakis(methylenephosphonic acid) ([hexane-1,6-diylbis[nitrilobis(methylene)]]tetrakisphosphonic acid) (HDTMP), and diethylenetriaminepenta(methylenephosphonic acid) ([(bis{2-[bis(phosphonomethyl)amino]ethyl}amino)methyl]phosphonic acid; DTPMP). The weight ratio of ammonium hydroxide to the etching inhibitor for the etching stop layer is 1:1 to 20:1, or may be 1:1 to 10:1, or may be 1:1 to 7.5:1, which can control the etching rate of the semiconductor cleaning composition for the post-etching residue, titanium component, metal lead, dielectric layer, and etching stop layer, improve the efficiency of removing the post-etching residue and titanium component, and help reduce the corrosiveness to the metal lead, dielectric layer, and etching stop layer.

[0032] The types and proportions of various materials in the semiconductor cleaning composition will be further described below. It should be particularly noted that the semiconductor cleaning composition of the present disclosure can achieve the technical effects of the present disclosure simply by complying with the above-mentioned blending proportions, and the semiconductor cleaning composition of the present disclosure is not limited to the types and proportions of the materials listed below.

[0033] The pH value of the mixture may be 6 to 10, or 6.5 to 9.5, or 7 to 9. By selecting ammonium hydroxide and adjusting the pH value of the mixture, it is possible to obtain a high etching rate for titanium components and improve the effect of inhibiting corrosion of aluminum components or other metals within an appropriate pH value range.

[0034] The weight ratio of hydrogen peroxide in the semiconductor cleaning composition may be 10% to 25%, or 15% to 25%, or 18% to 23%, based on the total weight of the semiconductor cleaning composition being 100%, thereby enabling the etching rate of the semiconductor cleaning composition for post-etching residues, titanium components, metal leads, dielectric layers, and etching stop layers to be further adjusted to meet different usage needs.

[0035] The organic solvent may be selected from the group consisting of alcohol solvents, ether solvents, alcohol ether solvents, sulfone solvents, amide solvents, pyrrolidone solvents, and imidazolidinone solvents, or the organic solvent may be methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol t-butyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol t-butyl ether, triethylene glycol dimethyl ether, or tetraethylene glycol Dimethyl ether, propylene glycol dimethyl ether, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol methyl butyl ether, dipropylene glycol monobutyl ether, 2,5,7,10-tetraoxaundecane, 4,7-dimethyl-2,5,9-trioxadecane, 4-methyl-2,5,9-trioxadecane, tetrahydrofurfuryl alcohol (THFA), dimethyl sulfoxideDMSO), dimethyl sulfone (dimethyl sulfone, sulfolane, N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), N,N-diethylformamide (DEF), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N-isobutyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidin-2-one (DMI), and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidin-2-one (DMPU). This allows you to select different organic solvents depending on the type of target substance you want to remove;

[0036] The mixture may further contain water, and the weight ratio of the organic solvent in the mixture may be 20% to 70%, or 25% to 65%, or 30% to 60%, or 35% to 55%, based on the total weight of the mixture being 100%. By adjusting the ratio of the organic solvent to the water, the corrosiveness of the semiconductor cleaning composition to aluminum components can be further reduced and the post-etching residue removal effect can be improved.

[0037] The mixture may further include a metal corrosion inhibitor, which may be an azole, and may be selected from the group consisting of benzotriazole (BTA), 2,2'-[[(methyl-1H-benzotriazole-1-yl)methyl]imino]bisethanol, 4-nitrobenzotriazole, 5-nitrobenzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole (5mBTA), 1-phenylbenzotriazole, benzotriazole-4-carboxylic acid, and benzotriazole-5-carboxylic acid. The metal corrosion inhibitor may be selected from the group consisting of 4-aminobenzotriazole, 5-aminobenzotriazole, hydroxybenzotriazole, 2-(5-aminopentyl)benzotriazole, and 5-phenylthiol-benzotriazole. The metal corrosion inhibitor may further protect the metal leads and reduce the corrosiveness of the semiconductor cleaning composition to the metal leads.

[0038] The mixture may further include a chelating agent. The chelating agent may include an amine carboxylic acid compound, and may be selected from the group consisting of glycine, alanine, cysteine, methionine, aspartic acid, asparagine, glutamic acid, glutamine, arginine, serine, histidine, iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), N-(2-carboxyethyl)iminodiacetic acid (N,N-bis(carboxymethyl)-β-alanine), ethylenediamine tetraacetic acid (EDTA), trans-1,2-diaminocyclohexane tetraacetic acid (CyDTA), triethylenetetramine hexaacetic acid (TTHA), diethylenetriamine pentaacetic acid (pentetic acid), and the like. acid;DTPA), 1,3-propanediaminetetraacetic acid (1,3-propanediamine-N,N,N',N'-tetraacetic acid;PDTA), 1,3-diamino-2-propanol-N,N,N',N'-tetraacetic acid (DPTA-OH), glycol ether diamine tetraacetic acid (glycol ether diamine tetraacetic acid;GEDTA), (S,S)-ethylenediamine-N,N'-disuccinic acid ((S,S)-ethylenediamine-N,N'-disuccinic acid;EDDS), hydroxyethylethylenediaminetriacetic acid (N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid;HEDTA), N,N-bis(2-hydroxyethyl)glycine (N,N'-bis(2-hydroxyethl)glycine;bicine and dicarboxymethyl glutamic acid (CMGA);

[0039] The chelating agent can be used to stabilize metal ions dissolved in the semiconductor cleaning composition during cleaning, such as titanium ions dissolved from the titanium component, and to form a relatively stable chelate by chelating with the metal ions. Therefore, the addition of the chelating agent can reduce the influence of the metal ions on the properties of the semiconductor cleaning composition, further improve the stability of each component in the semiconductor cleaning composition, and help maintain the etching rate of the semiconductor cleaning composition.

[0040] The weight ratio of ammonium hydroxide to the chelating agent is 1:1 to 1:20, or 1:1 to 1:15, or 1:1 to 1:10. By adjusting the ratio of ammonium hydroxide to the chelating agent, the stability of hydrogen peroxide in the semiconductor cleaning composition can be improved, the etching rate of the semiconductor cleaning composition for titanium components can be further improved, and the corrosiveness of the semiconductor cleaning composition for aluminum components or other metal structures can be reduced.

[0041] In order to enable those skilled in the art to fully utilize and practice the present disclosure without the need for undue interpretation, the present disclosure is further illustrated by the following specific examples, which should not be construed as limiting the scope of the present disclosure, but are merely used to illustrate how to carry out the materials and methods of the present disclosure. [Example]

[0042] <Production of semiconductor cleaning composition> See Tables 1-1 to 1-4 below. Tables 1-1 to 1-4 show the compositional components and proportions of the mixtures of Examples A1 to A19 and Comparative Examples A1 to A8, and the abbreviations of the selected materials are shown in Table 2 below.

[0043] [Table 1-1]

[0044] [Table 1-2]

[0045] [Table 1-3]

[0046] [Table 1-4]

[0047] [Table 2]

[0048] The mixtures of Examples A1 to A19 and Comparative Examples A1 to A8 were mixed with hydrogen peroxide to prepare semiconductor cleaning compositions of Examples B1 to B19 and Comparative Examples B1 to B8, and their pH values ​​are shown in Table 3 below. Specifically, the semiconductor cleaning compositions of Examples B1 to B19 and Comparative Examples B1 to B8 were prepared by mixing the corresponding mixtures with an aqueous hydrogen peroxide solution. The weight percent concentration of the aqueous hydrogen peroxide solution was 31%, and the weight ratio of the aqueous hydrogen peroxide solution to the mixture was 2:1. In the prepared semiconductor cleaning compositions, the weight ratios of hydrogen peroxide, water, and the mixture were approximately 20%, 47%, and 33%, respectively. It should be noted that the examples of the present disclosure are limited to specific hydrogen peroxide ratios. However, in actual applications, different hydrogen peroxide ratios can achieve the technical effects of the present disclosure. Therefore, the present disclosure is not limited to the formulations or ratios of the examples.

[0049] [Table 3]

[0050] <Etching rate of semiconductor cleaning compositions for different materials> The etching rates of the semiconductor cleaning compositions of Examples B1 to B6, Examples B13 to B15, Examples B17 to B19, and Comparative Examples B1 to B8 for different materials were measured below. The measurement method for this test was as follows: Each material was deposited on a blank wafer by a different deposition method, and the wafer after deposition was immersed in the semiconductor cleaning composition, maintaining a specific temperature during the immersion process and immersing for a certain period of time, and measuring the difference in wafer thickness before and after immersion to calculate the etching rate for each material.

[0051] The materials used in this test included titanium nitride, alumina (etch stop layer), copper metal, cobalt metal, and a low-k dielectric layer; the titanium nitride had a 30 second immersion time and thickness measured with an ellipsometer; the alumina had a 10 minute immersion time and thickness measured with an ellipsometer; the low-k dielectric layer had a 10 minute immersion time and thickness measured with an ellipsometer; and the copper metal and cobalt metal both had 10 minute immersion times and thickness measured with a four-point probe.

[0052] <Etching rate for titanium nitride and alumina> See Table 4 below. Table 4 shows the etching rates of the semiconductor cleaning compositions of Examples B1 to B6, Examples B13 to B15, Examples B17 to B19, and Comparative Examples B1 to B8 on titanium nitride and alumina.

[0053] [Table 4]

[0054] From the results in Table 4, it can be seen that the etching rate of titanium nitride of the semiconductor cleaning compositions of Examples B1 to B6, Examples B13 to B15, and Examples B17 to B19 can all be maintained at 170 Å per minute or more, proving that all of the above Examples can effectively remove titanium nitride. In addition, the semiconductor cleaning compositions of Comparative Examples B1 to B4 did not contain an etch stop layer etch inhibitor, so their alumina etching rates were also significantly higher than those of the other Examples. It is particularly noteworthy that in the semiconductor cleaning compositions of Comparative Examples B2 to B4, the water content was sequentially reduced (50 wt% to 55 wt%, 40 wt% to 45 wt%, and 30 wt% to 35 wt%, respectively), and thus the etching rate of alumina was slightly reduced, but this was not as effective as the addition of an etch stop layer etch inhibitor.

[0055] Furthermore, when the etching results of the semiconductor cleaning compositions of Example B1, Example B14, Comparative Example B6 and Comparative Example B7 were compared, it was found that the etching rate for titanium nitride was clearly improved when ammonium hydroxide was used.

[0056] <Etching rate for copper and cobalt metals> See Table 5 below. Table 5 shows the etching rates of the semiconductor cleaning compositions of Examples B5 to B7, B9, B13, B16 and B18 for copper metal and cobalt metal.

[0057] [Table 5]

[0058] From the results in Table 5, it was found that the etching rates of copper metal and cobalt metal of the semiconductor cleaning compositions of Examples B5 to B7, B9 and B13 were all 1 Å per minute or less. Also, it was found that the etching rates of the semiconductor cleaning compositions of Examples B16 and B18 for copper metal and cobalt metal could be changed by adding or not adding a chelating agent and adjusting the ratio of the chelating agent to alkali.

[0059] <Etching rate for dielectric layer> See Table 6 below. Table 6 shows the etching rates of the semiconductor cleaning compositions of Examples B1 to B3 on low-k dielectric layers.

[0060] [Table 6]

[0061] From the results in Table 6, it can be seen that the etching rates of the semiconductor cleaning compositions of Examples B1 to B3 against the low-k dielectric layer are all 1 Å per minute or less, proving that the semiconductor cleaning compositions are less corrosive to the dielectric layer.

[0062] <Continuous operation stability> The etching rate of the semiconductor cleaning compositions of Example B8 to Example B12 is measured when they are continuously operated for different periods of time. In this test, the wafer after deposition is immersed in the semiconductor cleaning composition, and the etching rate of titanium nitride and alumina is measured at different times. The results of this test are shown in Table 7 below.

[0063] [Table 7]

[0064] The results in Table 7 show that there is no obvious change in the etching rate of the semiconductor cleaning compositions of Examples B8 to B12 for titanium nitride and alumina under the condition of 48 hours of continuous operation, and it is proved that the semiconductor cleaning compositions can maintain a good etching rate even when operated continuously for a long period of time.

[0065] <Decomposition rate of hydrogen peroxide> The decomposition rate of hydrogen peroxide in the semiconductor cleaning compositions of Examples B4, B6, B7, B14, B15, B17, B18 and Comparative Examples B5 to B7 was measured below. In this test, a fixed amount of titanium nitride powder was dissolved in the semiconductor cleaning compositions, and the compositions were left in a hot water bath at 60°C for 4 hours. After that, oxidation and reduction were carried out with an aqueous potassium permanganate solution, and the change in the hydrogen peroxide concentration in the semiconductor cleaning compositions before and after the hot water bath was measured by titration. The results of this test are listed in Table 8 below.

[0066] [Table 8]

[0067] From the results in Table 8, it can be seen that the hydrogen peroxide decomposition rates of Examples B4, B6, B7, B14, B15, B17, and B18 were all 3.00% / hour or less. Furthermore, from Examples B4, B6, B7, B14, B15, and B18, it can be seen that the addition of a chelating agent can reduce the hydrogen peroxide decomposition rate of the semiconductor cleaning composition to 2.50% / hour or less, proving that the addition of a chelating agent causes the chelating agent and metal ions dissolved in the semiconductor cleaning composition to form a metal complex, preventing the metal ions from excessively catalyzing the decomposition reaction of hydrogen peroxide and maintaining the reactivity of hydrogen peroxide.

[0068] In the semiconductor cleaning composition of Comparative Example B5, the weight ratio of ammonium hydroxide to the etching stop layer etching inhibitor was less than 1:1, and the acid-alkalinity was not properly adjusted, so titanium nitride powder could not be effectively dissolved. In the semiconductor cleaning composition of Comparative Example B6, TEAH was added as an alkaline substance, but TEAH did not have a sufficient stabilizing effect on metal ions after dissolution, so titanium nitride powder could not be effectively dissolved even though the pH value of Comparative Example B6 was higher than 6. In the semiconductor cleaning composition of Comparative Example B7, TBAH was added as an alkaline substance, but the acid-alkalinity was not properly adjusted, so titanium nitride powder could not be effectively dissolved. Therefore, the titanium nitride solubility was poor in all of Comparative Examples B5 to B7.

[0069] As described above, the present disclosure selects specific types of compounds as components of semiconductor cleaning compositions, and adjusts the ratio of ammonium hydroxide and etch stop layer etch inhibitor therein, which helps to control the etching rate of the semiconductor cleaning composition on post-etch residues, titanium components, metal leads, dielectric layers and etch stop layers, improve the efficiency of removing post-etch residues and titanium components, and reduce the corrosiveness to metal leads, dielectric layers and etch stop layers.

[0070] Although the present disclosure has been disclosed as described above in the examples, they are not used to limit the present disclosure, and any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure should be based on that defined by the claims attached below. [Explanation of symbols]

[0071] 100: Method for cleaning semiconductor device 110, 120: Process 200: Cleaning equipment for semiconductor devices 210: Cleaning composition delivery device 220: Cleaning chamber 221: Rotating element

Claims

1. A method for cleaning a semiconductor device, comprising: providing a semiconductor cleaning composition comprising the mixture and hydrogen peroxide; contacting the semiconductor cleaning composition with a semiconductor device to clean the semiconductor device; Equipped with The semiconductor device includes a titanium component including at least one of titanium metal and a titanium-containing compound, and an aluminum component including at least one of aluminum metal and an aluminum-containing compound; the mixture includes ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor; the etch stop layer etch inhibitor is selected from the group consisting of (1-hydroxy-1-phosphonoethyl)phosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetrakis(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid); the weight ratio of the ammonium hydroxide to the etch stop layer etch inhibitor is 1:1 to 20:1; The etching rate of the semiconductor cleaning composition for the titanium component is 170 Å / min or more, and the etching rate of the semiconductor cleaning composition for the aluminum component is 1 Å / min or less.

2. 2. The method for cleaning a semiconductor device according to claim 1, wherein the step of contacting the semiconductor cleaning composition with the semiconductor device comprises spraying the semiconductor cleaning composition onto the surface of the semiconductor device while the semiconductor device is rotating.

3. A semiconductor device cleaning facility, a cleaning composition delivery device for providing a semiconductor cleaning composition comprising the mixture and hydrogen peroxide; a cleaning chamber communicating with the cleaning composition delivery device and configured to accommodate a semiconductor device; Equipped with The semiconductor cleaning composition contacts the semiconductor device in the cleaning chamber to clean the semiconductor device, and the semiconductor device includes a titanium component including at least one of titanium metal and a titanium-containing compound, and an aluminum component including at least one of aluminum metal and an aluminum-containing compound, the mixture includes ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor; the etch stop layer etch inhibitor is selected from the group consisting of (1-hydroxy-1-phosphonoethyl)phosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetrakis(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid); The weight ratio of the ammonium hydroxide to the etch stop layer etch inhibitor is 1:1 to 20:

1.

4. 4. The semiconductor device cleaning equipment of claim 3, wherein the cleaning chamber includes a rotating element on which the semiconductor device is placed, and the cleaning composition transport device sprays the semiconductor cleaning composition onto the surface of the semiconductor device while the semiconductor device is rotating.

5. A semiconductor cleaning composition comprising the mixture and hydrogen peroxide, the mixture includes ammonium hydroxide, an organic solvent, and an etch stop layer etch inhibitor; the etch stop layer etch inhibitor is selected from the group consisting of (1-hydroxy-1-phosphonoethyl)phosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), hexamethylenediaminetetrakis(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid); The semiconductor cleaning composition, wherein the weight ratio of the ammonium hydroxide to the etch stop layer etch inhibitor is 1:1 to 20:

1.

6. 6. The semiconductor cleaning composition according to claim 5, wherein the pH value of the mixture is 6 to 10.

7. 6. The semiconductor cleaning composition according to claim 5, wherein the weight ratio of the hydrogen peroxide in the semiconductor cleaning composition is 10% to 25%, with the total weight of the semiconductor cleaning composition being 100%.

8. 6. The semiconductor cleaning composition according to claim 5, wherein the organic solvent is selected from the group consisting of alcohol-based solvents, ether-based solvents, alcohol ether-based solvents, sulfone-based solvents, amide-based solvents, pyrrolidone-based solvents, and imidazolidinone-based solvents.

9. Examples of the organic solvent include methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol t-butyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol t-butyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, and propylene glycol methyl propyl ether. ether, propylene glycol methyl butyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol methyl butyl ether, dipropylene glycol monobutyl ether, 2,5,7,10-tetraoxaundecane, 4,7-dimethyl-2,5,9-trioxadecane, 4-methyl-2,5 6. The semiconductor cleaning composition according to claim 5, wherein the carboxylic acid is selected from the group consisting of 1,9-trioxadecane, tetrahydrofurfuryl alcohol, dimethyl sulfoxide, dimethyl sulfone, sulfolane, N,N-dimethylformamide, dimethylacetamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

10. 6. The semiconductor cleaning composition according to claim 5, wherein the mixture further contains water, and the weight ratio of the organic solvent in the mixture is 20% to 70% based on the total weight of the mixture being 100%.

11. The semiconductor cleaning composition of claim 5 , wherein the mixture further comprises a metal corrosion inhibitor.

12. 12. The semiconductor cleaning composition according to claim 11, wherein the metal corrosion inhibitor is selected from the group consisting of benzotriazole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, 4-nitrobenzotriazole, 5-nitrobenzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, 1-phenylbenzotriazole, benzotriazole-4-carboxylic acid, benzotriazole-5-carboxylic acid, 4-aminobenzotriazole, 5-aminobenzotriazole, hydroxybenzotriazole, 2-(5-aminopentyl)benzotriazole, and 5-phenylthiolbenzotriazole.

13. The semiconductor cleaning composition of claim 5 , wherein the mixture further comprises a chelating agent.

14. 14. The semiconductor cleaning composition according to claim 13, wherein the chelating agent is selected from the group consisting of glycine, alanine, cysteine, methionine, aspartic acid, asparagine, glutamic acid, glutamine, arginine, serine, histidine, iminodiacetic acid, nitrilotriacetic acid, N-(2-carboxyethyl)iminodiacetic acid, ethylenediaminetetraacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diaminetetraacetic acid, (S,S)-ethylenediamine-N,N'-disuccinic acid, hydroxyethylethylenediaminetriacetic acid, N,N-bis(2-hydroxyethyl)glycine, and dicarboxymethylglutamic acid.

Images